Title: Systems Approach of Photoisomerization Metrology for Single-Crystal Optical Actuators: A Case Study of [Ru(SO₂)(NH₃)₄Cl]Cl

Abstract

Chemicals that undergo photoisomerization in their single-crystal form may act as optical actuators or sensors. It is important to determine the molecular-scale characteristics of this photoisomerization as they govern the macroscopic nature of the optical phenomenon. In situ single-crystal X-ray diffraction has led the way in this field of characterization, with photoinduced crystal structures being realized via technical developments that have become known as “photocrystallography”. Single-crystal optical spectroscopy methods are less well developed in this research area, even though they provide synergistic information that is crucial for optimizing photoconversion levels in single-crystal optical actuators and enabling their comprehensive photoisomerization analysis. This paper demonstrates the importance of characterizing photoisomerism in crystalline media using a systems approach to photoisomerization metrology. Therefore, single-crystal optical spectroscopy, single-crystal Raman spectroscopy, and photocrystallography are concerted. The case study on [Ru(SO₂)(NH₃)₄Cl]Cl (1) demonstrates how this approach optimizes its photoconversion levels, using key parameters that are established by single-crystal optical absorption spectroscopy. These parameters furnish the design of single-crystal Raman spectroscopy and photocrystallography experiments which are needed for a comprehensive photoisomerization analysis of 1. Raman shifts identify photostructural changes in isolated bonds as a function of temperature. One such shift leads to the realization of a previously unidentifiedmore » photoisomer in 1, which is then confirmed by photocrystallography that renders its 3-D light-induced crystal structure. Both optical-spectroscopy methods are concerted with imaging to evidence photochromic changes in single crystals that occur upon photoisomerization and upon their thermal decay, whose characteristics are realized via single-crystal Raman spectroscopy. Overall, an end-to-end operational pipeline is showcased for more optimally characterizing the light-induced optical properties and structures of single-crystal optical actuators.« less

Authors:

Cole, Jacqueline M.  ^[1];

• Search DOE PAGES for author "Cole, Jacqueline M."
• Search DOE PAGES for ORCID "0000-0002-1552-8743"

Gosztola, David J.  ^[2];

• Search DOE PAGES for author "Gosztola, David J."
• Search DOE PAGES for ORCID "0000-0003-2674-1379"

Velazquez-Garcia, Jose J. ^[3]; Chen, Yu-Sheng ^[4]

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+ Show Author Affiliations

1. Univ. of Cambridge (United Kingdom). Cavendish Lab.; Science and Technology Facilities Council (STFC), Oxford (United Kingdom). Rutherford Appleton Lab. (RAL); Argonne National Lab. (ANL), Lemont, IL (United States)
2. Argonne National Lab. (ANL), Lemont, IL (United States)
3. Univ. of Cambridge (United Kingdom). Cavendish Lab.
4. Argonne National Lab. (ANL), Lemont, IL (United States). Advanced Photon Source (APS); Univ. of Chicago, Lemont, IL (United States)

Publication Date:

Fri Dec 11 00:00:00 EST 2020

Research Org.:

Argonne National Lab. (ANL), Argonne, IL (United States)

Sponsoring Org.:

USDOE Office of Science (SC), Basic Energy Sciences (BES); Science and Technology Facilities Council (STFC); Royal Commission of the Great Exhibition; National Science Foundation (NSF); National Council of Science and Technology of Mexico (CONACyT); Cambridge Trust

OSTI Identifier:

1756407

Grant/Contract Number:  

AC02-06CH11357; NSF/CHE-1346572; NSF/CHE-1834750; NSF/DMR-1531283

Resource Type:

Accepted Manuscript

Journal Name:

Journal of Physical Chemistry. C

Additional Journal Information:

Journal Volume: 124; Journal Issue: 51; Journal ID: ISSN 1932-7447

Publisher:

American Chemical Society

Country of Publication:

United States

Language:

English

Subject:

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY