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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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Publication details

The article was received on 11 Dec 2015, accepted on 11 Feb 2016 and first published on 11 Feb 2016


Article type: Paper
DOI: 10.1039/C5CE02434J
Citation: CrystEngComm, 2016,18, 4180-4187
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    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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