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Issue 22, 2016
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Raising the (metastable) bar: 100% photo-switching in [Pd(Bu4dien)(η1-[N with combining low line]O2)]+ approaches ambient temperature

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Abstract

100% nitro–nitrito linkage isomerism is reported in single-crystals of the Pd(II)–nitrite system [Pd(Bu4dien)(η1-[N with combining low line]O2)]BPh4 (Bu4dien = N,N,N′,N′-tetrabutyldiethylenetriamine, BPh4 = tetraphenylborate). Complete conversion to a metastable endo-nitrito-(η1-[O with combining low line]NO) isomer is achieved after just 15 min irradiation with 400 nm LED light. The system is entirely metastable below 240 K, while pseudo-steady-state photocrystallographic experiments confirm that the excited state isomer is retained, at substantial conversion levels, under continuous illumination until 260 K. These results show promise for new linkage isomer systems, based on heavier transition metal centres, which display full functionality under near-ambient conditions.

Graphical abstract: Raising the (metastable) bar: 100% photo-switching in [Pd(Bu4dien)(η1- [[N with combining low line]] O2)]+ approaches ambient temperature

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Supplementary files

Article information


Submitted
11 Dec 2015
Accepted
11 Feb 2016
First published
11 Feb 2016

This article is Open Access

CrystEngComm, 2016,18, 4180-4187
Article type
Paper
Author version available

Raising the (metastable) bar: 100% photo-switching in [Pd(Bu4dien)(η1-[N with combining low line]O2)]+ approaches ambient temperature

L. E. Hatcher, CrystEngComm, 2016, 18, 4180
DOI: 10.1039/C5CE02434J

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