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（TM）络合阳离子作为结构导向剂，通过溶剂热法制备并完成结构表征了一系列结构维度丰富的新型杂化卤化亚铜，其结构涵盖从一维（1D）带状结构到二维（2D）层状结构的多种形貌。化合物[TM(2,2'-联吡啶（2,2-bipy）)₃]Cu₅I₇（TM = Fe（1）、Co（2）和Ni（3））呈现为由[Cu₅I₁₀]结构单元通过共边相互连接形成的一维[Cu₅I₇]²⁻链状结构。在化合物[TM(2,2'-联吡啶)₂I]₂Cu₇I₉（TM = Mn（4）、Cu（5）和Ru（6））中，[Cu₅I₉]结构单元与[Cu₂I₆]二聚体交替通过共边连接，构筑得到一维[Cu₇I₉]²⁻链状结构。化合物[Cu(2,2'-联吡啶)₂I][二甲基-2,2'-联吡啶（(Me)₂-2,2-bipy）]Cu₈I₁₁（7）包含一种新型一维[Cu₈I₁₁]³⁻链状结构，该链由基于CuI₄四面体与CuI₃三角构型构建的复杂[Cu₈I₁₃]结构单元构成。化合物[Co(2,2'-联吡啶)₃]Cu₅Br₈（8）具有由[Cu₆Br₁₀]结构单元与线性[Cu₄Br₈]四聚体相互连接形成的一维[Cu₅Br₈]³⁻阴离子链结构。在化合物K[Mn(2,2'-联吡啶)₃]₂Cu₆I₁₁（9）中，[Cu₃I₇]次级结构单元直接相互连接形成二维[Cu₆I₁₁]⁵⁻层状结构；该层状结构进一步通过K⁺离子与I⁻之间的弱相互作用构筑出三维[K@Cu₆I₁₁]⁴⁻骨架，其内部拥有被[Mn(2,2'-联吡啶)₃]²⁺络合物占据的一维大尺寸通道。紫外-可见漫反射光谱测试结果显示，标题化合物均表现出半导体特性，带隙范围为1.44~1.95 eV；其中样品4、5和9在可见光辐照下对有机污染物的光催化降解活性显著优于氮掺杂P25。