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Light‐Induced Bistability in the 2 D Coordination Network {[Fe(bbtr) 3 ][BF 4 ] 2 } ∞ : Wavelength‐Selective Addressing of Molecular Spin States
Author(s) -
Chakraborty Pradip,
Pillet Sebastien,
Bendeif ElEulmi,
Enachescu Cristian,
Bronisz Robert,
Hauser Andreas
Publication year - 2013
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201301257
Subject(s) - bistability , spin crossover , crystallography , wavelength , optical bistability , spin (aerodynamics) , symmetry breaking , chemistry , condensed matter physics , materials science , molecular physics , physics , optics , nonlinear optics , optoelectronics , thermodynamics , quantum mechanics , laser
Whereas the neat polymeric Fe II compound {[Fe(bbtr) 3 ][ClO 4 ] 2 } ∞ (bbtr=1,4‐di(1,2,3‐triazol‐1‐yl)butane) shows an abrupt spin transition centered at 107 K facilitated by a crystallographic symmetry breaking, in the covalently linked 2D coordination network of {[Fe(bbtr) 3 ][BF 4 ] 2 } ∞ , Fe II stays in the high‐spin state down to 10 K. However, strong cooperative effects of elastic origin result in reversible, persistent, and wavelength‐selective photoswitching between the low‐spin and high‐spin manifolds. This compound thus shows true light‐induced bistability below 100 K. The persistent bidirectional optical switching behavior is discussed as a function of temperature, irradiation time, and intensity. Crystallographic studies reveal a photoinduced symmetry breaking and serve to establish the correlation between structure and cooperative effects. The static and kinetic behavior is explicated within the framework of the mean‐field approximation.