In:
Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, The Royal Society, Vol. 375, No. 2084 ( 2017-01-13), p. 20160033-
Abstract:
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) 3 Cl or Mn(2,2′-bipy-5,5′-dicarboxylic acid)(CO) 3 Br with LiCl or LiBr, respectively, produces single crystals of {Li 2 (DMF) 2 [(2,2′-bipy-5,5′-dicarboxylate)Re(CO) 3 Cl]} n ( ReLi ) or {Li 2 (DMF) 2 [(2,2′-bipy-5,5′-dicarboxylate)Mn(CO) 3 Br]} 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(2,2′-bipy-5,5′-dicarboxylate)(CO) 3 Cl ( ReLi ) or Mn(2,2′-bipy-5,5′- dicarboxylate)(CO) 3 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) 3 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’.
Type of Medium:
Online Resource
ISSN:
1364-503X
,
1471-2962
DOI:
10.1098/rsta.2016.0033
Language:
English
Publisher:
The Royal Society
Publication Date:
2017
detail.hit.zdb_id:
208381-4
detail.hit.zdb_id:
1462626-3
SSG:
11
SSG:
5,1
SSG:
5,21
Bookmarklink
