TY - JOUR

T1 - Relating Excited States to the Dynamics of Macroscopic Strain in Photoresponsive Crystals

AU - Ahmed, Ejaz

AU - Chizhik, Stanislav

AU - Sidelnikov, Anatoly

AU - Boldyreva, Elena

AU - Naumov, Panče

N1 - Funding Information: This work was financially supported by the Ministry of Science and Higher Education (projects AAAA-A21-121011390011-4 (E.B.) and 121032500059-4 (S.C., A.S.)), and by New York University Abu Dhabi (P.N., E.A.). Publisher Copyright: © 2022 American Chemical Society.

PY - 2022/2/28

Y1 - 2022/2/28

N2 - Exposure of a photoreactive single crystal to light with a wavelength offset from its absorption maximum can have two distinct effects. The first is the "direct"effect, wherein the excited state generated in individual chemical species is influenced. The second is the "indirect"effect, which describes the penetration of light into the crystal and hence the spatial propagation and completeness of transformation. We illustrate using the nitro-nitrito isomerization of [Co(NH3)5NO2]Cl(NO3) as an example that the direct and indirect effects can be independently determined. This is achieved by comparing the dynamics of macroscopic crystal deformation (bending curvature and crystal elongation) induced by the photochemical reaction when irradiating a crystal at the absorption maximum and at different band edges (above or below the maximum) of the same band. Quantitative description of the macroscopic strain dynamics in comparison with experiments allowed us to suggest that irradiation at different tails of the same absorption band causes isomerization to proceed via different excited states and an additional photochemical reaction (presumably, reverse nitrito-nitro isomerization) can occur on irradiation at the ligand-field band edges.

AB - Exposure of a photoreactive single crystal to light with a wavelength offset from its absorption maximum can have two distinct effects. The first is the "direct"effect, wherein the excited state generated in individual chemical species is influenced. The second is the "indirect"effect, which describes the penetration of light into the crystal and hence the spatial propagation and completeness of transformation. We illustrate using the nitro-nitrito isomerization of [Co(NH3)5NO2]Cl(NO3) as an example that the direct and indirect effects can be independently determined. This is achieved by comparing the dynamics of macroscopic crystal deformation (bending curvature and crystal elongation) induced by the photochemical reaction when irradiating a crystal at the absorption maximum and at different band edges (above or below the maximum) of the same band. Quantitative description of the macroscopic strain dynamics in comparison with experiments allowed us to suggest that irradiation at different tails of the same absorption band causes isomerization to proceed via different excited states and an additional photochemical reaction (presumably, reverse nitrito-nitro isomerization) can occur on irradiation at the ligand-field band edges.

UR - http://www.scopus.com/inward/record.url?scp=85125370146&partnerID=8YFLogxK

U2 - 10.1021/acs.inorgchem.1c03607

DO - 10.1021/acs.inorgchem.1c03607

M3 - Article

C2 - 35170305

AN - SCOPUS:85125370146

VL - 61

SP - 3573

EP - 3585

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 8

ER -