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Photochemistry of framework-supported M(diimine)(CO)₃X complexes in 3D Lithium-Carboxylate metal−organic frameworks: monitoring the effect of framework cations

机译:3D羧酸锂金属有机骨架中骨架支撑的M(diimine)(CO)₃X配合物的光化学:监测骨架阳离子的作用

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摘要

The structures and photochemical behaviour of two new metal-organic frameworks are reported. Reaction of Re(2,2ʹ-bipyʹ-5,5ʹ-dicarboxylic acid)(CO)₃Cl or Mn(2,2ʹ-bipyʹ-5,5ʹ- dicarboxylic acid)(CO)₃Br with either LiCl or LiBr, respectively, produces single crystals of {Li₂(DMF)₂[(2,2ʹ-bipyʹ-5,5ʹ-dicarboxylate)Re(CO)₃Cl]}n (ReLi) or {Li₂(DMF)₂[(2,2ʹ-bipyʹ- 5,5ʹ-dicarboxylate)Mn(CO)₃Br]}n (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(2,2ʹ-bipyʹ-5,5ʹ-dicarboxylate)(CO)₃Cl (ReLi) or Mn(2,2ʹ-bipyʹ-5,5ʹ- dicarboxylate)(CO)₃Br (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 infra-red measurements, are closer in behaviour to that of unsubstituted [Re(bipy)(CO)₃Cl] rather than a related MOF where the Li(I) cations are replaced by Mn(II) cations. These observations are further supported by DFT 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.
机译:报道了两种新的金属有机骨架的结构和光化学行为。 Re(2,2ʹ-联吡啶-5,5ʹ-二羧酸)(CO)₃Cl或Mn(2,2ʹ-联吡啶-5,5ʹ-二羧酸)(CO)₃Br分别与LiCl或LiBr反应{Li 2(DMF)2 [(2,2′-bipyʹ-5,5′-二羧酸盐)Re(CO)3 Cl]} n(ReLi)的单晶或{Li 2(DMF)2 [(2,2′-bipyʹ-5 ,5′-二羧酸酯)Mn(CO)= Br]} n(MnLi)。由两个MOF形成的结构包含一元羧酸桥联的Li(I)阳离子链,该链通过Re(2,2ʹ-bipyʹ-5,5ʹ-二羧酸酯)(CO)₃Cl(ReLi)单元交联或Mn(2,2ʹ-联吡啶-5,5ʹ-二羧酸盐)(CO)₃Br(MnLi)。研究了ReLi和MnLi的光物理和光化学行为。含rh的MOF ReLi表现出发光,并且通过时间分辨的红外测量确定其激发态行为,其行为更接近于未取代的[Re(bipy)(CO)₃Cl],而不是相关的MOF。其中Li(I)阳离子被Mn(II)阳离子取代。 DFT计算进一步支持了这些观察结果。激发后,MnLi形成二羰基物质,该二羰基物质会与离解的CO快速重组,其方式与大多数光喷射CO不会逸出MOF通道的方式一致。

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