School of Chemistry, Norwich Research Park, University of East Anglia , Norwich NR4 7TJ, United Kingdom.
Department of Chemistry, University of Oxford , Chemistry Research Laboratory, Oxford OX1 3TA, United Kingdom.
Struct Dyn. 2016 Jan 14;3(2):023608. doi: 10.1063/1.4940222. eCollection 2016 Mar.
In this work, the timescales and mechanisms associated with the structural dynamics of butadiyne-linked porphyrin dimers are investigated through time resolved narrowband pump/broadband probe transient absorption spectroscopy. Our results confirm previous findings that the broadening is partly due to a distribution of structures with different (dihedral) angular conformations. Comparison of measurements with excitations on the red and blue sides of the Q-band unravel the ground and excited state conformational re-equilibration timescales. Further comparison to a planarized dimer, through the addition of a ligand, provides conclusive evidence for the twisting motion performed by the porphyrin dimer in solution.
在这项工作中,通过时间分辨窄带泵/宽带探针瞬态吸收光谱研究了丁二炔连接的卟啉二聚体结构动力学的时间尺度和机制。我们的结果证实了先前的发现,即展宽部分是由于具有不同(二面角)构象的结构分布所致。将测量结果与 Q 带的红边和蓝边激发进行比较,揭示了基态和激发态构象再平衡的时间尺度。通过添加配体与平面化二聚体进行进一步比较,为卟啉二聚体在溶液中进行的扭转运动提供了确凿的证据。