Low-Dimensional Hybrid Cuprous Halides Directed by Transition Metal Complex: Syntheses, Crystal Structures, and Photocatalytic Properties

By using transitional metal (TM)
complex cations as structure-directing
agents, a series of new hybrid cuprous halides with abundant architectures
ranging from one-dimensional (1D) ribbons to two-dimensional (2D)
layers have been solvothermally prepared and structurally characterized.
Compounds [TM­(2,2-bipy)3]­Cu5I7 (TM
= Fe (1), Co (2), and Ni (3)) feature 1D [Cu5I7]2– chains
formed by the interconnection of [Cu5I10] units
via edge-sharing. In compounds [TM­(2,2-bipy)2I]2Cu7I9 (TM = Mn (4), Cu (5), and Ru (6)), the [Cu5I9] units and [Cu2I6] dimers are alternately
interlinked via edge-sharing to form the 1D [Cu7I9]2– chains. Compound [Cu­(2,2-bipy)2I]­[(Me)2-2,2-bipy]­Cu8I11 (7) contains
a new 1D [Cu8I11]3– chain
composed of complex [Cu8I13] units based on
CuI4 tetrahedra and CuI3 triangles. Compound
[Co­(2,2-bipy)3]­Cu5Br8 (8) features 1D [Cu5Br8]3– anionic
chain built from the interconnection of [Cu6Br10] units and linear [Cu4Br8] tetramers. In compound
K­[Mn­(2,2-bipy)3]2Cu6I11 (9), the [Cu3I7] secondary building
units are directly interconnected to form 2D [Cu6I11]5– layers, which are further interconnected
by K+ ions via weak K–I bonds to generate a 3D [K@Cu6I11]4– framework with 1D large
channels occupied by [Mn­(2,2-bipy)3]2+ complexes.
The UV–vis diffuse reflectance measurements reveal that the
title compounds possess semiconductor behaviors with smaller band
gaps of 1.44–1.95 eV, and samples 4, 5, and 9 show highly efficient photocatalytic degradation
activities over organic pollutant than N-doped P25 under visible-light
irradiation.

以过渡金属（Transitional Metal, TM）配合物阳离子作为结构导向剂，通过溶剂热法制备了一系列结构新颖的杂化卤化亚铜材料，其结构维度覆盖一维（1D）带状结构至二维（2D）层状结构，并完成了系统的结构表征。化合物[TM(2,2'-联吡啶, 2,2-bipy)₃]Cu₅I₇（TM=铁(1)、钴(2)、镍(3)）具有一维[Cu₅I₇]²⁻链结构，该链由[Cu₅I₁₀]结构单元通过边共享方式连接而成。在化合物[TM(2,2'-联吡啶, 2,2-bipy)₂I]₂Cu₇I₉（TM=锰(4)、铜(5)、钌(6)）中，[Cu₅I₉]结构单元与[Cu₂I₆]二聚体通过边共享交替连接，构筑出一维[Cu₇I₉]²⁻链。化合物[Cu(2,2'-联吡啶, 2,2-bipy)₂I][(二甲基-2,2'-联吡啶, (Me)₂-2,2-bipy)]Cu₈I₁₁(7)含有一种新型一维[Cu₈I₁₁]³⁻链，该链由基于CuI₄四面体与CuI₃三角形构筑的[Cu₈I₁₃]复杂结构单元构成。化合物[钴(2,2'-联吡啶, 2,2-bipy)₃]Cu₅Br₈(8)具有一维[Cu₅Br₈]³⁻阴离子链，该链由[Cu₆Br₁₀]结构单元与线性[Cu₄Br₈]四聚体连接而成。在化合物K[锰(2,2'-联吡啶, 2,2-bipy)₃]₂Cu₆I₁₁(9)中，[Cu₃I₇]次级结构单元直接连接形成二维[Cu₆I₁₁]⁵⁻层，随后K⁺离子通过弱K-I键进一步将这些层连接，得到具有一维大孔道的三维[K@Cu₆I₁₁]⁴⁻骨架，孔道内填充有[Mn(2,2'-联吡啶, 2,2-bipy)₃]²⁺配合物。紫外-可见漫反射光谱测试表明，所有目标化合物均表现出半导体特性，其禁带宽度介于1.44~1.95 eV之间；其中样品4、5和9在可见光照射下对有机污染物的光催化降解活性优于氮掺杂P25。