Isomerization and rearrangement of boriranes: from chemical rarities to functional materials

Mellerup, Soren K.; Wang, Suning

doi:10.1007/s40843-018-9306-8

Cited by 19 publications

(19 citation statements)

References 67 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…As the products/intermediates in the photoinduced reactions of four‐coordinate N,C‐chelate organoboron compounds, borirane species, such as A ppy ‐S 0 and A iba ‐S 0 in this work, are regarded as a new type of promising photoresponsive materials . Calculations to clarify the rich photophysical and photochemical properties of the borirane species are currently under way.…”

Section: Resultsmentioning

confidence: 98%

Theoretical Study on Photoisomerization Mechanisms of Diphenyl‐Substituted N,C‐Chelate Organoboron Compounds

2020

Chemistry A European J

View full text Add to dashboard Cite

N,C-chelate organoboron compounds are widely employed as photoresponsive and optoelectronic materials due to their efficient photochromic reactivity.I tw as found in experimentst hat two diphenyl-substituted organoboron compounds, namely B(ppy)Ph 2 (ppy = 2-phenylpyridyl) and B(iba)Ph 2 (iba = N-isopropylbenzylideneamine), show distinct photochemicalr eactivity.B (ppy)Ph 2 is inert on irradiation, whereas B(iba)Ph 2 undergoes photoinduced transformations, yieldingB N-cyclohepta-1,3,5-triene via ab orirane intermediate. In this work, the complete actives pace self-consistent field and its second-order perturbation (CASPT2//CASSCF) methodsw ere used to investigate the photoinduced reaction mechanisms of B(ppy)Ph 2 and B(iba)Ph 2 .T he calculations showed that the two compounds isomerize to borirane in the same way by passing at ransition state in the S 1 state and ac onicali ntersection between the S 1 and S 0 states.T he energyb arriers in the S 1 state of 0.54 and 0.26 eV for B(ppy)Ph 2 and B(iba)Ph 2 ,respectively,were explained by analyzing the charge distributionso fm inima in S 0 and S 1 states. The resultsp rovide helpful insights into the excited-state dynamics of organoboron compounds, which could assist in rationald esign of boron-basedp hotoresponsive materials.

show abstract

Section: Resultsmentioning

confidence: 98%

Theoretical Study on Photoisomerization Mechanisms of Diphenyl‐Substituted N,C‐Chelate Organoboron Compounds

2020

Chemistry A European J

View full text Add to dashboard Cite

show abstract

“…Among the numerous photoresponsive systems, organoboron compounds exhibit substantial photochemical activity and find a wide range of uses in optoelectronic fields including molecular switches, optical data storage, and logic technologies . In 2005, Kawashima et al.…”

Section: Introductionmentioning

confidence: 99%

“…[5][6][7] Among the numerous photoresponsive systems, organoboron compounds exhibit substantial photochemical activity and find a wide range of uses in optoelectronic fields including molecular switches, optical data storage, and logic technologies. [8][9][10] In 2005, Kawashima et al reported the photochromic process of a catechol borane compound (E)-29 containing a BÀ N coordinate bond, which was caused by the dissociation of a BÀ N bond and the subsequent trans-cis isomerization of the azo group. [11] In 2008, Wang and coworkers discovered that N,C-chelate organoboron compound B (ppy)Mes 2 (ppy = 2-phenylpyridine, Mes = mesityl) undergoes thermally reversible phototransformation around the boron core to achieve a base-stabilized borirane with a three-membered ring comprising one boron and two carbon atoms (see Scheme 1), accompanied by a distinct color switching from light yellow to dark green.…”

Section: Introductionmentioning

confidence: 99%

Insights into the Photoinduced Isomerization Mechanisms of a N,C–Chelate Organoboron Compound: A Theoretical Study

Zhu

2020

ChemPhysChem

View full text Add to dashboard Cite

As the first discovered organoboron compound with photochromic property, B(ppy)Mes2 (ppy=2‐phenylpyridine, Mes=mesityl) displays rich photochemistry that constitutes a solid foundation for wide applications in optoelectronic fields. In this work, we investigated the B(ppy)Mes2 to borirane isomerization mechanisms in the three lowest electronic states (S0, S1, and T1) based on the complete active space self‐consistent field (CASSCF) and its second‐order perturbation (CASPT2) methods combined with time‐dependent density functional theory (TD‐DFT) calculations. Our results show that the photoisomerization in the S1 state is dominant, which is initiated by the cleavage of the B‐Cppy bond. After overcoming a barrier of 0.5 eV, the reaction pathway leads to a conical intersection between the S1 and S0 states (S1/S0)x, from which the decay path may go back to the reactant B(ppy)Mes2 via a closed‐shell intermediate (Int1‐S0) or to the product borirane via a biradical intermediate (Int2‐S0). Although triplet states are probably involved in the photoinduced process, the possibility of the photoisomerization in T1 state is very small owing to the weakly allowed S1→T1 intersystem crossing and the high energy barrier (0.77 eV). In addition, we found the photoisomerization is thermally reversible, which is consistent with the experimental observations.

show abstract

“…In contrast to organic photochromic materials, inorganic photochromic materials have many advantages such as excellent mechanical strength and chemical and thermal stabilities [40,41]. Various inorganic photochromic materials such as metal oxides (MoO 3 , WO 3 , and V 2 O 5 ), ferroelectrics (Na 0.5 Bi 2.5 Nb 2 O 9 and Bi 4 Ti 3 O 12 ), and other robust oxides (Mg 2 SnO 4 and Sr 2 SnO 4 ) have been developed [15,[42][43][44][45][46]. Among inorganic photochromic materials, metal oxides suffer from a slow response time and a poor reversibility [25,47].…”

Section: Introductionmentioning

confidence: 99%

Reversible multiplexing for optical information recording, erasing, and reading-out in photochromic BaMgSiO4:Bi3+ luminescence ceramics

et al. 2020

View full text Add to dashboard Cite

Optical data storage technology has many advantages over the traditional solid-state and magnetic storage technology, such as low cost, multi-dimensional storage, and rewritable capability. Therefore, the optical data storage technology has been in increasing demand for optical storage media. Herein, the photochromic and photoluminescence properties of BaMgSiO 4 :Bi 3+ ceramics were investigated. The BaMgSiO4:Bi3+ ceramics showed reversible photochromism from gray to pink upon alternating the 254 nm ultraviolet light and 532 nm laser irradiation. This is caused by the electron trapping and de-trapping in the oxygen vacancies of the BaMgSiO 4 :Bi 3+ host. This reversible behavior of photochromism was applied to fabricate different patterns on the surface of the BaMgSiO 4 :Bi 3+ ceramics, which exhibited the reversible dual-mode optical information recording and erasing abilities. The photoluminescence reversible modulation of the BaMgSiO 4 :Bi 3+ ceramics was obtained through the photochromic phenomenon. This modification behavior of luminescence could be applied to read-out the recording information in the BaMgSiO 4 :Bi 3+ ceramics. The coloration and bleaching of BaMgSiO 4 :Bi 3+ ceramics were dependent on the time of light stimulation, which facilitated multiplexing encoding. This photoluminescence and photochromism multiplexing of the BaMgSiO 4 :Bi 3+ ceramics enhanced the optical data storage capability.

show abstract

Isomerization and rearrangement of boriranes: from chemical rarities to functional materials

Cited by 19 publications

References 67 publications

Theoretical Study on Photoisomerization Mechanisms of Diphenyl‐Substituted N,C‐Chelate Organoboron Compounds

Theoretical Study on Photoisomerization Mechanisms of Diphenyl‐Substituted N,C‐Chelate Organoboron Compounds

Insights into the Photoinduced Isomerization Mechanisms of a N,C–Chelate Organoboron Compound: A Theoretical Study

Reversible multiplexing for optical information recording, erasing, and reading-out in photochromic BaMgSiO4:Bi3+ luminescence ceramics

Contact Info

Product

Resources

About