Reade Thomas J, Murphy Thomas S, Calladine James A, Horvath Raphael, Clark Ian P, Greetham Gregory M, Towrie Michael, Lewis William, George Michael W, Champness Neil R
School of Chemistry, University of Nottingham, Nottingham NG7 2RD, UK.
STFC Rutherford Appleton Lab, Central Laser Facility, Didcot OX11 0QX, UK.
Philos Trans A Math Phys Eng Sci. 2017 Jan 13;375(2084). doi: 10.1098/rsta.2016.0033.
The structures and photochemical behaviour of two new metal-organic frameworks (MOFs) are reported. Reaction of Re(2,2'-bipy-5,5'-dicarboxylic acid)(CO)Cl or Mn(2,2'-bipy-5,5'-dicarboxylic acid)(CO)Br with LiCl or LiBr, respectively, produces single crystals of {Li(DMF) [(2,2'-bipy-5,5'-dicarboxylate)Re(CO)Cl]} ( RELI: ) or {Li(DMF)[(2,2'-bipy-5,5'-dicarboxylate)Mn(CO)Br]} ( MNLI: ). The structures formed by the two MOFs comprise one-dimensional chains of carboxylate-bridged Li(I) cations that are cross-linked by units of Re(2,2'-bipy-5,5'-dicarboxylate)(CO)Cl ( RELI: ) or Mn(2,2'-bipy-5,5'- dicarboxylate)(CO)Br ( MNLI: ). The photophysical and photochemical behaviour of both RELI: and MNLI: are probed. The rhenium-containing MOF, RELI: , exhibits luminescence and the excited state behaviour, as established by time-resolved infrared measurements, is closer in behaviour to that of unsubstituted [Re(bipy)(CO)Cl] rather than a related MOF where the Li(I) cations are replaced by Mn(II) cations. These observations are further supported by density functional theory calculations. Upon excitation MNLI: forms a dicarbonyl species which rapidly recombines with the dissociated CO, in a fashion consistent with the majority of the photoejected CO not escaping the MOF channels.This article is part of the themed issue 'Coordination polymers and metal-organic frameworks: materials by design'.
报道了两种新型金属有机框架（MOF）的结构和光化学行为。Re(2,2'-联吡啶-5,5'-二羧酸)(CO)Cl或Mn(2,2'-联吡啶-5,5'-二羧酸)(CO)Br分别与LiCl或LiBr反应，生成{Li(DMF) [(2,2'-联吡啶-5,5'-二羧酸根)Re(CO)Cl]}（RELI: ）或{Li(DMF)[(2,2'-联吡啶-5,5'-二羧酸根)Mn(CO)Br]}（MNLI: ）的单晶。这两种MOF形成的结构包含由羧酸根桥连的Li(I)阳离子构成的一维链，这些链通过Re(2,2'-联吡啶-5,5'-二羧酸根)(CO)Cl（RELI: ）或Mn(2,2'-联吡啶-5,5'-二羧酸根)(CO)Br（MNLI: ）单元交联。对RELI: 和MNLI: 的光物理和光化学行为进行了探究。含铼的MOF，RELI: ，表现出发光现象，并且通过时间分辨红外测量确定，其激发态行为在行为上更接近未取代的[Re(bipy)(CO)Cl]，而不是Li(I)阳离子被Mn(II)阳离子取代的相关MOF。密度泛函理论计算进一步支持了这些观察结果。激发后，MNLI: 形成一种二羰基物种，该物种迅速与解离的CO重新结合，其方式与大多数光致喷射的CO未逸出MOF通道一致。本文是主题为“配位聚合物和金属有机框架：设计材料”特刊的一部分。
