碘化亚铜配位聚合物的单光子和双光子激发发光

{ "defaultlang": "zh", "titlegroup": { "articletitle": [ { "lang": "zh", "data": [ { "name": "text", "data": "碘化亚铜配位聚合物的单光子和双光子激发发光" } ] }, { "lang": "en", "data": [ { "name": "text", "data": "One- and Two-photon Excited Photoluminescence of Cuprous Iodide Coordination Polymer" } ] } ] }, "contribgroup": { "author": [ { "name": [ { "lang": "zh", "surname": "尹", "givenname": "少云", "namestyle": "eastern", "prefix": "" }, { "lang": "en", "surname": "YIN", "givenname": "Shao-yun", "namestyle": "western", "prefix": "" } ], "stringName": [], "aff": [ { "rid": "aff1", "text": "1" }, { "rid": "aff2", "text": "2" } ], "role": [ "first-author" ], "bio": [ { "lang": "zh", "text": [ "尹少云(1985－), 女, 山东德州人, 博士, 实验师, 2019年于中山大学获得博士学位, 主要从事发光材料的测试方法的研究。E-mail:shao_yun_111@163.com" ], "graphic": [], "data": [ [ { "name": "bold", "data": [ { "name": "text", "data": "尹少云" } ] }, { "name": "text", "data": "(1985－), 女, 山东德州人, 博士, 实验师, 2019年于中山大学获得博士学位, 主要从事发光材料的测试方法的研究。E-mail:" }, { "name": "text", "data": "shao_yun_111@163.com" } ] ] } ], "email": "shao_yun_111@163.com", "deceased": false }, { "name": [ { "lang": "zh", "surname": "莫", "givenname": "钧婷", "namestyle": "eastern", "prefix": "" }, { "lang": "en", "surname": "MO", "givenname": "Jun-ting", "namestyle": "western", "prefix": "" } ], "stringName": [], "aff": [ { "rid": "aff1", "text": "1" } ], "role": [], "deceased": false }, { "name": [ { "lang": "zh", "surname": "潘", "givenname": "梅", "namestyle": "eastern", "prefix": "" }, { "lang": "en", "surname": "PAN", "givenname": "Mei", "namestyle": "western", "prefix": "" } ], "stringName": [], "aff": [ { "rid": "aff1", "text": "1" } ], "role": [ "corresp" ], "corresp": [ { "rid": "cor1", "lang": "en", "text": "PAN Mei, E-mail:panm@mail.sysu.edu.cn", "data": [ { "name": "text", "data": "PAN Mei, E-mail:panm@mail.sysu.edu.cn" } ] } ], "bio": [ { "lang": "zh", "text": [ "潘梅(1976－), 女, 山东济南人, 博士, 教授, 博士研究生导师, 2004年于中国科学院上海技术物理研究所获得博士学位, 主要从事金属-有机发光材料的设计、机制与性能的研究。E-mail:panm@mail.sysu.edu.cn" ], "graphic": [], "data": [ [ { "name": "bold", "data": [ { "name": "text", "data": "潘梅" } ] }, { "name": "text", "data": "(1976－), 女, 山东济南人, 博士, 教授, 博士研究生导师, 2004年于中国科学院上海技术物理研究所获得博士学位, 主要从事金属-有机发光材料的设计、机制与性能的研究。E-mail:" }, { "name": "text", "data": "panm@mail.sysu.edu.cn" } ] ] } ], "email": "panm@mail.sysu.edu.cn", "deceased": false } ], "aff": [ { "id": "aff1", "intro": [ { "lang": "zh", "label": "1", "text": "中山大学 化学学院, 广东 广州 510275", "data": [ { "name": "text", "data": "中山大学 化学学院, 广东 广州 510275" } ] }, { "lang": "en", "label": "1", "text": "School of Chemistry, Sun Yat-Sen University, Guangzhou 510275, China", "data": [ { "name": "text", "data": "School of Chemistry, Sun Yat-Sen University, Guangzhou 510275, China" } ] } ] }, { "id": "aff2", "intro": [ { "lang": "zh", "label": "2", "text": "广东工业大学 分析测试中心, 广东 广州 510006", "data": [ { "name": "text", "data": "广东工业大学 分析测试中心, 广东 广州 510006" } ] }, { "lang": "en", "label": "2", "text": "Analysis and Test Center, Guangdong University of Technology, Guangzhou 510006, China", "data": [ { "name": "text", "data": "Analysis and Test Center, Guangdong University of Technology, Guangzhou 510006, China" } ] } ] } ] }, "abstracts": [ { "lang": "zh", "data": [ { "name": "p", "data": [ { "name": "text", "data": "利用两种半柔性的π-不饱和双吡啶端基配体与CuI配位，分别通过结构转化法和原位组装法，得到两种具有{[CuIL]·solvents}" }, { "name": "sub", "data": [ { "name": "italic", "data": [ { "name": "text", "data": "n" } ] } ] }, { "name": "text", "data": "结构通式的二维和三维碘化亚铜配位聚合物，分别命名为Cu-3和Cu-4。利用X射线单晶衍射、X射线粉末衍射和元素分析等表征方法确定了Cu-3和Cu-4的结构信息。研究这两种配位聚合物的光物理性能发现，用紫外光激发时，Cu-3和Cu-4均表现出单一发射峰，最大波长分别为513 nm的蓝绿光和555 nm的黄色光，归属于卤素到配体的电荷转移（" }, { "name": "sup", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "XLCT）。同时，这两种配位聚合物均表现出双光子激发发光性质，有望应用于生物成像领域。" } ] } ] }, { "lang": "en", "data": [ { "name": "p", "data": [ { "name": "text", "data": "Through structural transition method or " }, { "name": "italic", "data": [ { "name": "text", "data": "in-situ" } ] }, { "name": "text", "data": " assembly method, two semi-flexible π-conjugated unsaturated bipodal-ligands were coordinated with CuI to obtain 2-D or 3-D cuprous iodide coordination polymerizations with the general structure of {[CuIL]·solvents}" }, { "name": "sub", "data": [ { "name": "italic", "data": [ { "name": "text", "data": "n" } ] } ] }, { "name": "text", "data": ", namely Cu-3 and Cu-4, respectively. The structural information of Cu-3 and Cu-4 was determined by X-ray single crystal diffraction, powder X-ray diffraction and elemental analysis. Studying the photophysical properties of these two coordination polymers revealed that when excited by ultraviolet light, Cu-3 and Cu-4 showed a single emission peak with blue-green light at 513 nm and yellow light at 555 nm, respectively, which were attributed to halogen to ligand charge transfer (" }, { "name": "sup", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "XLCT) state. At the same time, these two coordination polymers both exhibit two-photon excited luminescence properties, and are expected to be used in the field of biological imaging." } ] } ] } ], "keyword": [ { "lang": "zh", "data": [ [ { "name": "text", "data": "碘化亚铜" } ], [ { "name": "text", "data": "配位聚合物" } ], [ { "name": "text", "data": "卤素到配体电荷转移" } ], [ { "name": "text", "data": "双光子发光" } ] ] }, { "lang": "en", "data": [ [ { "name": "text", "data": "cuprous iodide" } ], [ { "name": "text", "data": "coordination polymer" } ], [ { "name": "text", "data": "XLCT" } ], [ { "name": "text", "data": "two-photon luminescence" } ] ] } ], "highlights": [], "body": [ { "name": "sec", "data": [ { "name": "sectitle", "data": { "label": [ { "name": "text", "data": "1" } ], "title": [ { "name": "text", "data": "引言" } ], "level": "1", "id": "s1" } }, { "name": "p", "data": [ { "name": "text", "data": "金属有机光功能材料由于在有机发光二极管" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "1", "type": "bibr", "rid": "b1", "data": [ { "name": "text", "data": "1" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "5", "type": "bibr", "rid": "b5", "data": [ { "name": "text", "data": "5" } ] } } ], "rid": [ "b1", "b2", "b3", "b4", "b5" ], "text": "1-5", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "、传感器和转换器" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "6", "type": "bibr", "rid": "b6", "data": [ { "name": "text", "data": "6" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "7", "type": "bibr", "rid": "b7", "data": [ { "name": "text", "data": "7" } ] } } ], "rid": [ "b6", "b7" ], "text": "6-7", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "、防伪条形码" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "8", "type": "bibr", "rid": "b8", "data": [ { "name": "text", "data": "8" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "、生物成像和治疗" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "9", "type": "bibr", "rid": "b9", "data": [ { "name": "text", "data": "9" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "10", "type": "bibr", "rid": "b10", "data": [ { "name": "text", "data": "10" } ] } } ], "rid": [ "b9", "b10" ], "text": "9-10", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "、光通讯和光调制" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "11", "type": "bibr", "rid": "b11", "data": [ { "name": "text", "data": "11" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "13", "type": "bibr", "rid": "b13", "data": [ { "name": "text", "data": "13" } ] } } ], "rid": [ "b11", "b12", "b13" ], "text": "11-13", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "等诸多方面具有重要的应用前景，从而得到科学家们的广泛关注和研究。近些年来，由于在化学、物理、生物等研究领域具有独特的性能和应用，铜配合物以及铜簇化合物一直是科学家们研究的热点。特别是d" }, { "name": "sup", "data": [ { "name": "text", "data": "10" } ] }, { "name": "text", "data": "电子构型的亚铜配合物由于具有丰富的光化学和光物理性质而得到特别的关注。在众多的研究体系中，卤化铜(I)聚集体是目前处于配位化学和晶体工程前沿的一个重要的研究领域。卤化铜(I)的聚集体可以用一个通式来表示：CU" }, { "name": "italic", "data": [ { "name": "sub", "data": [ { "name": "text", "data": "x" } ] } ] }, { "name": "italic", "data": [ { "name": "text", "data": "X" }, { "name": "sub", "data": [ { "name": "text", "data": "y" } ] } ] }, { "name": "italic", "data": [ { "name": "text", "data": "L" }, { "name": "sub", "data": [ { "name": "text", "data": "z" } ] } ] }, { "name": "text", "data": "(其中" }, { "name": "italic", "data": [ { "name": "text", "data": "X" } ] }, { "name": "text", "data": "=Cl，Br或I；" }, { "name": "italic", "data": [ { "name": "text", "data": "L" } ] }, { "name": "text", "data": "=N，S或P基有机配体)，可以作为独立的结构单元存在，也可以以Cu" }, { "name": "italic", "data": [ { "name": "text", "data": "X" } ] }, { "name": "text", "data": "为构建块嵌入配位聚合物" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "14", "type": "bibr", "rid": "b14", "data": [ { "name": "text", "data": "14" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。铜的配位数一般有2，3，4几种，对应典型的线形、三角形和四面体配位模式，而具有强配位能力的卤素离子可以作为端基或" }, { "name": "italic", "data": [ { "name": "text", "data": "μ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": " ~" }, { "name": "italic", "data": [ { "name": "text", "data": "μ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "8" } ] }, { "name": "text", "data": "桥连基团与亚铜离子配位。基于以上两点，卤化铜(I)聚集体呈现出丰富的结构多样性和优异的光学性质" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "15", "type": "bibr", "rid": "b15", "data": [ { "name": "text", "data": "15" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "31", "type": "bibr", "rid": "b31", "data": [ { "name": "text", "data": "31" } ] } } ], "rid": [ "b15", "b16", "b17", "b18", "b19", "b20", "b21", "b22", "b23", "b24", "b25", "b26", "b27", "b28", "b29", "b30", "b31" ], "text": "15-31", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。除了常见的经由单光子吸收路径的紫外激发发光，近年来，利用近红外光激发的双光子发光和上转换发光也获得了广泛的关注。众所周知，近红外光有更好的聚焦深度、生物组织穿透能力和较小的细胞损伤等优势，适合生物等领域的应用。因而，设计合成能够有效吸收近红外光并通过双光子激发路径发射可见光的铜配合物金属-有机材料，也是一个重要的研究课题。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "卤化铜(I)聚集体可以通过各种途径来制备，但该类化合物的合成难点在于结晶过程的不可控制，在该过程中，聚集体通过构型或构象的转变从溶液相转变为晶体相。在结晶状态下，卤化铜聚集体的生长强烈地依赖于晶体学对称性，生成具有一定拓扑结构的产物。因而，有机配体的选择，如：电荷、尺寸以及构型等是构筑不同结构的卤化铜聚集体的关键因素" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "22", "type": "bibr", "rid": "b22", "data": [ { "name": "text", "data": "22" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。本文分别通过结构转化法和原位组装法，得到3位和4位吡啶端基半柔性π-不饱和双吡啶端基配体3-pmbtd和4-pmbtd与CuI配位构造的两种不同结构的碘化亚铜配位聚合物。测试了其紫外单光子和近红外双光子激发的发光性质。实验发现，两种配位聚合物均具有较好的双光子激发发光性质。" } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "label": [ { "name": "text", "data": "2" } ], "title": [ { "name": "text", "data": "实验" } ], "level": "1", "id": "s2" } }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "label": [ { "name": "text", "data": "2.1" } ], "title": [ { "name": "text", "data": "试剂与仪器" } ], "level": "2", "id": "s2-1" } }, { "name": "p", "data": [ { "name": "text", "data": "试剂：3-氨甲基吡啶，3-(Aminomethyl)pyridine，纯度97%，Macklin；4-甲氨基吡啶，4-(Aminomethyl)pyridine，纯度98%，Macklin；碘化亚铜，Copper(I) iodide，CuI，纯度98%，百灵威科技；双环(2.2.2)辛-7-烯-2, 3, 5, 6-四羧酸二酐，bicyclo(2.2.2)oct-7-ene-2, 3, 5, 6-tetracarboxylic acid dianhydride(BTD)，纯度98%，百灵威科技；N'N-二甲基甲酰胺(DMF)、乙醇(EtOH)、乙腈(CH" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "CN)和二氯甲烷(CH" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "Cl" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": ")购于天津市大茂化学试剂厂，AR级，直接使用未经其他处理。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "仪器：Bruker AVANCE Ⅲ 400(400 MHz)型核磁共振波谱仪(德国Bruker公司)；RigaKu SmartLab X射线粉末衍射仪(日本理学公司)；Perkin-Elmer 240型元素分析仪(美国Perkin-Elmer公司)；NETZSCH-TG 209 F3 Tarsus热重分析仪(德国耐驰公司)；UV-3600 plus紫外-可见分光光度计(日本岛津公司)；Nicolet FT-IR-170SX傅里叶变换红外光谱仪，KBr压片法(4 000~400 cm" }, { "name": "sup", "data": [ { "name": "text", "data": "-1" } ] }, { "name": "text", "data": "，美国TemoSinic公司)；Edinburgh FLS 980荧光光谱仪(英国爱丁堡公司)；Astrella/OperaSolo飞秒激光器(美国Flucent Ltd.)，QE65 Pro光谱仪(海洋光学公司)。" } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "label": [ { "name": "text", "data": "2.2" } ], "title": [ { "name": "text", "data": "样品制备" } ], "level": "2", "id": "s2-2" } }, { "name": "p", "data": [ { "name": "text", "data": "配体3-pmbtd和4-pmbtd的合成参考文献[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "32", "type": "bibr", "rid": "b32", "data": [ { "name": "text", "data": "32" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "33", "type": "bibr", "rid": "b33", "data": [ { "name": "text", "data": "33" } ] } } ], "rid": [ "b32", "b33" ], "text": "32-33", "type": "bibr" } }, { "name": "text", "data": "]，合成路线如" }, { "name": "xref", "data": { "text": "图 1", "type": "fig", "rid": "Figure1", "data": [ { "name": "text", "data": "图 1" } ] } }, { "name": "text", "data": "。称取1.24 g(5 mmol)双环[2.2.2]辛-7-烯-2, 3, 5, 6-四羧酸二酐(BTD)置于25 mL的圆底烧瓶中。加入10 mL N’N-二甲基甲酰胺(DMF)溶剂，加热到160 ℃，搅拌至BTD完全溶解。再加入1.1 mL(11 mmol) 3-氨甲基吡啶或4-氨甲基吡啶，回流6 h。停止加热，旋蒸，分离出大部分DMF，静置过夜。次日，有大量的白色固体析出。抽滤，用少量乙醇清洗，再用大量乙醚冲洗。70 ℃烘箱干燥过夜，得大量白色粉末样品，产率分别为78.5%和70.7%。" }, { "name": "sup", "data": [ { "name": "text", "data": "1" } ] }, { "name": "text", "data": "H NMR(400 MHz, CDCL" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": ")：3-pmbtd：8.52(dd, " }, { "name": "italic", "data": [ { "name": "text", "data": "J" } ] }, { "name": "text", "data": "=6.6, 1.8, 2H), 7.60(dd, " }, { "name": "italic", "data": [ { "name": "text", "data": "J" } ] }, { "name": "text", "data": "=6.0, 1.9, 1H), 7.21(dd, " }, { "name": "italic", "data": [ { "name": "text", "data": "J" } ] }, { "name": "text", "data": "=7.8, 4.8, 1H), 5.87(dd, " }, { "name": "italic", "data": [ { "name": "text", "data": "J" } ] }, { "name": "text", "data": "=4.3, 3.1, 1H), 4.55(s, 2H), 3.75(s, 1H), 2.99(s, 2H)。4-pmbtd：8.53 (d, " }, { "name": "italic", "data": [ { "name": "text", "data": "J" } ] }, { "name": "text", "data": "=5.1 Hz, 2H), 7.15(s, 2H), 5.97(s, 1H), 4.54(s, 2H), 3.80(s, 1H), 3.04 (s, 2H)。" } ] }, { "name": "fig", "data": { "id": "Figure1", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图1" } ], "title": [ { "name": "text", "data": "配体3-pmbtd和4-pmbtd的合成路线" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig 1" } ], "title": [ { "name": "text", "data": "Synthesis route of 3-pmbtd and 4-pmbtd ligand" } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=2963238&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=2963238&type=small", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=2963238&type=middle" } ] } }, { "name": "p", "data": [ { "name": "text", "data": "合成配合物{[CuI(3-pmbtd)]·DMF}" }, { "name": "sub", "data": [ { "name": "italic", "data": [ { "name": "text", "data": "n" } ] } ] }, { "name": "text", "data": "(Cu-3)：称取100 mg Cu" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "I" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "配合物" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "33", "type": "bibr", "rid": "b33", "data": [ { "name": "text", "data": "33" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "至25 mL锥形瓶中，加入10 mL DMF溶剂，超声至Cu" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "I" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "配合物完全溶解。静置几天，瓶底析出浅棕色块状晶体，产率35%。EA：C" }, { "name": "sub", "data": [ { "name": "text", "data": "27" } ] }, { "name": "text", "data": "H" }, { "name": "sub", "data": [ { "name": "text", "data": "27" } ] }, { "name": "text", "data": "CuIN" }, { "name": "sub", "data": [ { "name": "text", "data": "5" } ] }, { "name": "text", "data": "O" }, { "name": "sub", "data": [ { "name": "text", "data": "5" } ] }, { "name": "text", "data": ", 理论值：C, 46.17; H, 3.66;N, 8.13。测定值：C, 46.47; H, 3.49; N, 8.28。IR(KBr, cm" }, { "name": "sup", "data": [ { "name": "text", "data": "-1" } ] }, { "name": "text", "data": ")：3 455(m), 1 768(m), 1 705(vs), 1 557(w), 1 431(m), 1 399(s), 1 347(s), 1 320 (m), 1 178(s), 767(m), 711(s)。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "合成配合物[CuI(4-pmbtd)]" }, { "name": "sub", "data": [ { "name": "italic", "data": [ { "name": "text", "data": "n" } ] } ] }, { "name": "text", "data": "·solvents (Cu-4)：称取4.3 mg(0.01 mmol)4-pmbtd配体，溶解于10 mL CH" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "Cl" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "中。将溶液过滤到试管中，再加入二氯甲烷和乙腈(" }, { "name": "italic", "data": [ { "name": "text", "data": "V" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "CH" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "Cl" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] } ] }, { "name": "text", "data": ":" }, { "name": "italic", "data": [ { "name": "text", "data": "V" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "CH" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "CN" } ] }, { "name": "text", "data": "=2:1)的混合溶剂3 mL至试管中，将溶解了3.8 mg(0.05 mmol)CuI的5 mL乙腈溶液过滤到上述试管中。静置几天，试管壁上长出无色块状晶体，产率45%。EA：[C" }, { "name": "sub", "data": [ { "name": "text", "data": "24" } ] }, { "name": "text", "data": "H" }, { "name": "sub", "data": [ { "name": "text", "data": "20" } ] }, { "name": "text", "data": "CuIN" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "O" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "·H" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "O·CH" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "CN]" }, { "name": "sub", "data": [ { "name": "italic", "data": [ { "name": "text", "data": "n" } ] } ] }, { "name": "text", "data": ", 理论值：C, 45.06%;H, 3.71%;N, 9.46%。测定值：C, 45.02%;H, 3.67%;N, 9.47%。IR(KBr, cm" }, { "name": "sup", "data": [ { "name": "text", "data": "-1" } ] }, { "name": "text", "data": ")：3 445(m), 1 771(w), 1 705(vs), 1 513(w), 1 423(s), 1 398(s), 1 363(w), 1 341(m), 1 319(w), 1 178(m), 923(m)。" } ] } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "label": [ { "name": "text", "data": "3" } ], "title": [ { "name": "text", "data": "结果与讨论" } ], "level": "1", "id": "s3" } }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "label": [ { "name": "text", "data": "3.1" } ], "title": [ { "name": "text", "data": "Cu-3和Cu-4的单晶结构" } ], "level": "2", "id": "s3-1" } }, { "name": "p", "data": [ { "name": "text", "data": "晶体Cu-3是通过结构转化法，将具有“立方烷”结构的Cu" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "I" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "零维小分子" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "33", "type": "bibr", "rid": "b33", "data": [ { "name": "text", "data": "33" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "溶解在DMF中静置几天而获得。单晶结构解析可以看出，Cu-3结晶于单斜晶系，" }, { "name": "italic", "data": [ { "name": "text", "data": "P" } ] }, { "name": "text", "data": "2" }, { "name": "sub", "data": [ { "name": "text", "data": "1" } ] }, { "name": "italic", "data": [ { "name": "text", "data": "m" } ] }, { "name": "text", "data": "滑移空间群(" }, { "name": "xref", "data": { "text": "表 1", "type": "table", "rid": "Table1", "data": [ { "name": "text", "data": "表 1" } ] } }, { "name": "text", "data": ")。在晶体解析过程中，发现分子是无序的，以" }, { "name": "italic", "data": [ { "name": "text", "data": "ac" } ] }, { "name": "text", "data": "面为平面，沿着" }, { "name": "italic", "data": [ { "name": "text", "data": "b" } ] }, { "name": "text", "data": "方向滑移。其不对称单元由一个亚铜离子、一个碘离子、一个3-pmbtd配体以及一个晶格DMF溶剂分子组成。其中亚铜离子是四配位的，呈现四面体的几何构型。配位原子来自于两个抗衡阴离子(I" }, { "name": "sup", "data": [ { "name": "text", "data": "-" } ] }, { "name": "text", "data": ")以及3-pmbtd配体的两个端基吡啶氮原子。Cu—I距离约为0.270 5 nm和0.276 5 nm，Cu—N距离约为0.206 3 nm和0.211 1 nm(" }, { "name": "xref", "data": { "text": "表 2", "type": "table", "rid": "Table2", "data": [ { "name": "text", "data": "表 2" } ] } }, { "name": "text", "data": ")。在Cu-3中，我们可以清楚地看到，出现在零维小分子" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "33", "type": "bibr", "rid": "b33", "data": [ { "name": "text", "data": "33" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "中的Cu" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "I" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "簇分解转化为螺旋状的一维(CuI)" }, { "name": "sub", "data": [ { "name": "sup", "data": [ { "name": "text", "data": "n" } ] } ] }, { "name": "text", "data": "链，进一步与配体自组装形成了二维平面结构。在Cu-3中，与金属配位的配体两端没有收敛到同一个金属离子上，而是与其他的亚铜离子交错配位，这样减小了分子间的空间位阻，有利于高维度的框架形成。2D层间结构进一步通过分子间的相互作用力堆积形成3D网状结构，如" }, { "name": "xref", "data": { "text": "图 2", "type": "fig", "rid": "Figure2", "data": [ { "name": "text", "data": "图 2" } ] } }, { "name": "text", "data": "所示。" } ] }, { "name": "table", "data": { "id": "Table1", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "表1" } ], "title": [ { "name": "text", "data": "配合物Cu-3和Cu-4的晶体学数据和结构精修总表" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Table 1" } ], "title": [ { "name": "text", "data": "Crystal data and structure refinement for Cu-3 and Cu-4" } ] } ], "note": [], "table": [ { "head": [ [ { "align": "center", "style": "class:table_top_border", "data": [ { "name": 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"http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=2963251&type=small", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=2963251&type=middle" } ] } }, { "name": "p", "data": [ { "name": "xref", "data": { "text": "图 4(a)", "type": "fig", "rid": "Figure4", "data": [ { "name": "text", "data": "图 4(a)" } ] } }, { "name": "text", "data": "为Cu-3和Cu-4的X射线粉末衍射测试谱图。我们发现，Cu-3和Cu-4的粉末衍射谱图与单晶衍射模拟的谱图一致，说明样品均为纯相。" } ] }, { "name": "fig", "data": { "id": "Figure4", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图4" } ], "title": [ { "name": "text", "data": "Cu-3和Cu-4粉末的单晶模拟衍射图(a)和热重曲线(b)" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig 4" } ], "title": [ { "name": "text", "data": "Simulated and as-synthesized X-ray diffration(a) and TGA curves(b) of Cu-3 and Cu-4" } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=2963263&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=2963263&type=small", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=2963263&type=middle" } ] } } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "label": [ { "name": "text", "data": "3.2" } ], "title": [ { "name": "text", "data": "Cu-3和Cu-4的热稳定性" } ], "level": "2", "id": "s3-2" } }, { "name": "p", "data": [ { "name": "text", "data": "Cu-3和Cu-4的热重谱图见" }, { "name": "xref", "data": { "text": "图 4(b)", "type": "fig", "rid": "Figure4", "data": [ { "name": "text", "data": "图 4(b)" } ] } }, { "name": "text", "data": "。在" }, { "name": "xref", "data": { "text": "图 4(b)", "type": "fig", "rid": "Figure4", "data": [ { "name": "text", "data": "图 4(b)" } ] } }, { "name": "text", "data": "中，35~186 ℃的失重对应Cu-3晶体中DMF分子的失去，在187~330 ℃之间出现一个平台，表明Cu-3配合物在这个温度段骨架结构可以稳定存在，主要的失重过程发生在330~400 ℃，对应于网络结构的分解。在35~190 ℃的失重对应Cu-4晶体中溶剂分子的失去，在200~315 ℃之间出现一个平台，表明Cu-4配合物在这个温度段骨架结构可以保持稳定，主要的失重过程发生在315~410 ℃，对应于网络结构的分解。上述数据表明，两种碘化亚铜配位聚合物均有较好的热稳定性。" } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "label": [ { "name": "text", "data": "3.3" } ], "title": [ { "name": "text", "data": "单光子激发发光" } ], "level": "2", "id": "s3-3" } }, { "name": "p", "data": [ { "name": "text", "data": "如" }, { "name": "xref", "data": { "text": "图 5(a)", "type": "fig", "rid": "Figure5", "data": [ { "name": "text", "data": "图 5(a)" } ] } }, { "name": "text", "data": "所示，配体3-pmbtd和4-pmbtd的固体紫外-可见吸收光谱图类似。200~300 nm之间的吸收归属于π-π" }, { "name": "sup", "data": [ { "name": "text", "data": "*" } ] }, { "name": "text", "data": "跃迁，300~400 nm的吸收归属于有机配体分子的特征n-π " }, { "name": "sup", "data": [ { "name": "text", "data": "*" } ] }, { "name": "text", "data": "跃迁。两种碘化亚铜配位聚合物的紫外-可见吸收均比对应的配体的吸收红移，在200 ~500 nm范围内有较宽的吸收，表明配位聚合物有较好的吸光能力。" } ] }, { "name": "fig", "data": { "id": "Figure5", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图5" } ], "title": [ { "name": "text", "data": "(a) 配体和配位聚合物的固体紫外-可见吸收光谱；(b)Cu-3和Cu-4的固体激发和发射光谱(室温)。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig 5" } ], "title": [ { "name": "text", "data": "(a)Solid-state UV-visible absorption spectra. (b)Photoluminescence spectra of Cu-3 and Cu-4(RT)." } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=2963269&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=2963269&type=small", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=2963269&type=middle" } ] } }, { "name": "p", "data": [ { "name": "text", "data": "如" }, { "name": "xref", "data": { "text": "图 5(b)", "type": "fig", "rid": "Figure5", "data": [ { "name": "text", "data": "图 5(b)" } ] } }, { "name": "text", "data": "所示，在常温下，用350 nm的紫外光激发Cu-3配合物，发射出最大波长在513 nm的蓝绿光，归属于激发三线态卤素到配体的电荷转移(" }, { "name": "sup", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "XLCT)。用330 nm的光激发，Cu-4发射出最大波长为555 nm的黄光，归属于卤素到配体的电荷转移跃迁(" }, { "name": "sup", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "XLCT)。Cu-3和Cu-4的量子产率分别为10.0%(" }, { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "ex" } ] }, { "name": "text", "data": "=350 nm)和0.2%(" }, { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "ex" } ] }, { "name": "text", "data": "= 330 nm)。相比于Cu-3而言，Cu-4配位聚合物的量子产率相对低一些。可能是由于聚合物中存在大量的溶剂分子，尤其是Cu-4中存在大量的溶剂水分子，羟基振动导致非辐射失活加剧。" } ] }, { "name": "p", "data": [ { "name": "xref", "data": { "text": "图 6", "type": "fig", "rid": "Figure6", "data": [ { "name": "text", "data": "图 6" } ] } }, { "name": "text", "data": "为Cu-3和Cu-4的变温激发和发射光谱。可以看到，不管在室温还是低温下，最大激发和发射峰位基本不变，只是强弱的变化。表明温度改变，配位聚合物的发射能级基本不变，仍然只表现出来自于" }, { "name": "sup", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "XLCT态的单发射，这与Cu" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "I" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "零维小分子" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "33", "type": "bibr", "rid": "b33", "data": [ { "name": "text", "data": "33" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "中的温度依赖双发射性质也是不同的。" } ] }, { "name": "fig", "data": { "id": "Figure6", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图6" } ], "title": [ { "name": "text", "data": "Cu-3(a)和Cu-4(b)的固体变温激发和发射光谱" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig 6" } ], "title": [ { "name": "text", "data": "(Temperature-dependent photoluminescence spectra of Cu-3(a) and Cu-4(b)" } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=2963276&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=2963276&type=small", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=2963276&type=middle" } ] } }, { "name": "p", "data": [ { "name": "text", "data": "对Cu-3和Cu-4各自的最大发射波长处分别进行发光寿命衰减曲线测试。结果表明，300K下，两个配合物的发光寿命分别为12.01 μs和10.26 μs微秒量级的寿命证实了来自于" }, { "name": "sup", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "XLCT态的三重态发光属性。在77 K下，由于热振动损耗的减弱，Cu-3和Cu-4的发光寿命均稍有增长，分别为16.86 μs和16.95μs。" } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "label": [ { "name": "text", "data": "3.4" } ], "title": [ { "name": "text", "data": "近红外双光子激发发光" } ], "level": "2", "id": "s3-4" } }, { "name": "p", "data": [ { "name": "text", "data": "考虑到Cu-3和Cu-4配位聚合物在可见至近红外区有较宽吸收，且近红外波段的光激发相比紫外激发在生物方面有着一定优越性，因此我们在室温下尝试了其双光子激发发光测试。结果表明，Cu-3和Cu-4在700~750 nm波段都能被较好激发。以750 nm激发为例进行说明。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "用飞秒激光器作为光源，测试Cu-3和Cu-4的双光子激发发光光谱，结果如" }, { "name": "xref", "data": { "text": "图 7", "type": "fig", "rid": "Figure7", "data": [ { "name": "text", "data": "图 7" } ] } }, { "name": "text", "data": "和" }, { "name": "xref", "data": { "text": "图 8", "type": "fig", "rid": "Figure8", "data": [ { "name": "text", "data": "图 8" } ] } }, { "name": "text", "data": "所示。在750 nm激光激发下，Cu-3发射出最大发射峰位于515 nm的蓝绿光，Cu-4发射出最大波长为565 nm的黄光(" }, { "name": "xref", "data": { "text": "图 7(a)", "type": "fig", "rid": "Figure7", "data": [ { "name": "text", "data": "图 7(a)" } ] } }, { "name": "text", "data": "和" }, { "name": "xref", "data": { "text": "图 8(a)", "type": "fig", "rid": "Figure8", "data": [ { "name": "text", "data": "图 8(a)" } ] } }, { "name": "text", "data": ")，分别与各自的固体单光子激发发光光谱类似。随着功率增大，Cu-3和Cu-4的发光强度增大，光源功率对荧光强度的关系曲线斜率分别为1.957和1.991，接近2(" }, { "name": "xref", "data": { "text": "图 7(b)", "type": "fig", "rid": "Figure7", "data": [ { "name": "text", "data": "图 7(b)" } ] } }, { "name": "text", "data": "和" }, { "name": "xref", "data": { "text": "图 8(b)", "type": "fig", "rid": "Figure8", "data": [ { "name": "text", "data": "图 8(b)" } ] } }, { "name": "text", "data": ")，表明均为双光子吸收过程。通过激光能量对发光强度的关系曲线，计算得到双光子吸收阈值为66.1 μJ和78.3 μJ，相对较小(" }, { "name": "xref", "data": { "text": "图 7(c)", "type": "fig", "rid": "Figure7", "data": [ { "name": "text", "data": "图 7(c)" } ] } }, { "name": "text", "data": "和" }, { "name": "xref", "data": { "text": "图 8(c)", "type": "fig", "rid": "Figure8", "data": [ { "name": "text", "data": "图 8(c)" } ] } }, { "name": "text", "data": ")。" } ] }, { "name": "fig", "data": { "id": "Figure7", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图7" } ], "title": [ { "name": "text", "data": "(a) 不同功率下Cu-3的双光子激发发光光谱图(" }, { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "ex" } ] }, { "name": "text", "data": " =750 nm)；(b)激发功率与发光强度关系曲线；(c)双光子激发阈值的计算。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig 7" } ], "title": [ { "name": "text", "data": "(a)Power-dependent emission spectra of Cu-3 under two-photon excitation(" }, { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "ex" } ] }, { "name": "text", "data": " =750 nm). (b)lg" }, { "name": "italic", "data": [ { "name": "text", "data": "I" } ] }, { "name": "text", "data": "-lg" }, { "name": "italic", "data": [ { "name": "text", "data": "P" } ] }, { "name": "text", "data": " relationship. (c)Change in slope of emission intensity for two-photon excitation threshold determination." } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=2963278&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=2963278&type=small", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=2963278&type=middle" } ] } }, { "name": "fig", "data": { "id": "Figure8", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图8" } ], "title": [ { "name": "text", "data": "(a) 不同功率下Cu-4的双光子激发发光光谱图(" }, { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "ex" } ] }, { "name": "text", "data": " =750 nm)；(b)激发功率与发光强度关系曲线；(c)双光子激发阈值的计算。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig 8" } ], "title": [ { "name": "text", "data": "(a)Power-dependent emission spectra of Cu-4 under two-photon excitation(" }, { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "ex" } ] }, { "name": "text", "data": " =750 nm). (b)lg" }, { "name": "italic", "data": [ { "name": "text", "data": "I" } ] }, { "name": "text", "data": "-lg" }, { "name": "italic", "data": [ { "name": "text", "data": "P" } ] }, { "name": "text", "data": " relationship. (c)Change in slope of emission intensity for two-photon excitation threshold determination." } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=2963281&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=2963281&type=small", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=2963281&type=middle" } ] } }, { "name": "p", "data": [ { "name": "text", "data": "上述结果表明，Cu-3和Cu-4都具有明显的双光子激发发光性能，并且具有相对较低的双光子激发阈值，有望应用于生物成像等领域。" } ] } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "label": [ { "name": "text", "data": "4" } ], "title": [ { "name": "text", "data": "结论" } ], "level": "1", "id": "s4" } }, { "name": "p", "data": [ { "name": "text", "data": "通过结构转化法和原位组装法，分别利用3位和4位吡啶端基的配体3-pmbtd和4-pmbtd与CuI配位组装，得到两种具有{[CuIL]·solvents}" }, { "name": "sub", "data": [ { "name": "italic", "data": [ { "name": "text", "data": "n" } ] } ] }, { "name": "text", "data": "结构通式的碘化亚铜配位聚合物。由于配体空间构象的不同，两种配位聚合物表现出不同的结构特点。在Cu-3中，形成(CuI)" }, { "name": "sub", "data": [ { "name": "italic", "data": [ { "name": "text", "data": "n" } ] } ] }, { "name": "text", "data": "一维链，3-pmbtd以螺旋的方式连接于两条相邻的(CuI)" }, { "name": "sub", "data": [ { "name": "italic", "data": [ { "name": "text", "data": "n" } ] } ] }, { "name": "text", "data": "链上，形成3D结构。而在Cu-4中，是以(Cu" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "I" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": ")菱形二聚体为次级结构单元，4-pmbtd作为桥连配体，形成2D平面结构。不同的结构特性所体现的光物理性质也不同。Cu-3在350 nm紫外光激发下发射出蓝绿光(" }, { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "em" } ] }, { "name": "text", "data": "=513 nm)，Cu-4在330 nm紫外光激发下发射出黄色光(" }, { "name": "italic", "data": [ { "name": "text", "data": "λ" } ] }, { "name": "sub", "data": [ { "name": "text", "data": "em" } ] }, { "name": "text", "data": "=555 nm)。两种配位聚合物均表现出双光子激发发光的特性。在750 nm光激发下，Cu-3和Cu-4发射出与紫外光激发类似的蓝绿光和黄光，并且具有较低的双光子激发阈值，具有在生物成像方面的应用潜力。" } ] } ] } ], "footnote": [], "reflist": { "title": [ { "name": "text", "data": "参考文献" } ], "data": [ { "id": "b1", "label": "1", "citation": [ { "lang": "en", "text": [ { "name": "text", "data": "GATHER M C, KÖHNEN A, MEERHOLZ K. 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