Abstract Polymer‐based room‐temperature‐phosphorescent (RTP) materials are attractive alternatives to low‐molecular‐weight organic RTP compounds because they can form self‐standing transparent films with high thermal stability. However, their lifetimes in air usually short (<≈0.4 s). Here, the simple amorphous polymer, poly(styrene sulfonic acid) (PSS), exhibits an ultralong lifetime when desiccated. The maximum is 1.22 s, which three times that of previously reported polymers. be...

Reorganization energy (λ1) in the ionization process of organic amines and that (λ2) electron attaching amine cation radicals are evaluated with AM1, ab initio MO, DFT methods, where dimethylaniline, methyldiphenylamine, triphenylamine adopted as a model hole transport material. The total λ value (=λ1 + λ2) decreases order dimethylaniline > methyldiphenylamine triphenylamine, which agrees well an increasing experimentally reported mobility diamines dimers above-mentioned amines,...

C−H bond activations of benzene and methane by M(η2-O2CH)2 (M = Pd or Pt) are theoretically investigated with density functional theory (DFT), MP2-MP4(SDQ), CCSD(T) methods. The activation takes place energies (Ea) 16.1 21.2 kcal/mol reaction (ΔE) −16.5 −25.8 for M Pt, respectively, to afford M(η2-O2CH)(C6H5)(η1-HCOOH), where MP4(SDQ) values given hereafter a negative ΔE value represents that the is exothermic. proceeds Ea 21.5 17.3 −8.3 −13.3 M(η2-O2CH)(CH3)(η1-HCOOH). However, Pd(PH3)2...

Simple yet ubiquitous multimolecular assembly systems with color-tunable emissions are realized by cooperative electron donor–acceptor interactions, such as the boron–nitrogen (B–N) dative bond a Lewis acid–base pair and charge transfer (CT) interactions. These ternary-component consisting of naphthalenediimide derivative (NDI), tris(pentafluorophenyl)borane (TPFB), aromatic molecules (guest) an NDI:TPFB:guest ratio 1:2:2. The crystal shows guest-dependent deep blue to orange when guest...

A detailed theoretical investigation was performed on all of the transition states and intermediates involved in Si−H oxidative addition H−SiR3 (R = H, Cl, or Me) to Pt(PH3)2, ethylene insertion into Pt−H Pt−SiR3 bonds, isomerization product, Si−C C−H reductive eliminations. In a Chalk−Harrod mechanism, rate-determining step is Pt(SiR3)(C2H5)(PH3) formed by bond its activation barrier 22 kcal/mol for R 23 Me, 26 Cl (MP4SDQ values are given hereafter). modified Pt−SiH3 44 H Me 60 Cl. Thus, it...

We studied the effects of concentration and location azobenzene chromophores on photoinduced deformation crosslinked liquid-crystalline polymers (CLCPs). The in CLCP affects degree isomerization moieties macroscopic behaviour films while determines contraction force length.

Rh-catalyzed hydrosilylation of ethylene was theoretically investigated with the DFT, MP4(SDQ), and CCSD(T) methods, where RhCl(PH3)3 adopted as a model catalyst. The rate-determining step in Chalk−Harrod mechanism is Si−C reductive elimination, activation barrier (Ea) which 27.4 (28.8) kcal/mol, values without parenthesis are calculated DFT MP4(SDQ) respectively. modified either insertion into Rh−SiMe3 bond (Ea = 13.5 (16.9) kcal/mol) at level or oxidative addition HSiMe3 =15.7 (11.3)...

The Cp(2)Zr-catalyzed hydrosilylation of ethylene was theoretically investigated with DFT and MP2-MP4(SDQ) methods, to clarify the reaction mechanism characteristic features this reaction. Although insertion into Zr-SiH(3) bond Cp(2)Zr(H)(SiH(3)) needs a very large activation barrier 41.0 (42.3) kcal/mol, is easily inserted Zr-H small 2.1 (2.8) where energy calculated DFT(B3LYP) method are given in parentheses those values which have been corrected for zero-point energy, hereafter. Not only...

A new reversible isomerization cycle for meta-ferrocenylazobenzene accomplished by combination of a single green light (546 nm) and redox change between Fe(II) Fe(III) was discovered. In the state, trans-to-cis proceeded upon irradiation exciting metal-to-ligand charge transfer (MLCT) in high quantum yield (Phit-->c = 0.51) which exceeds that azobenzene 0.12 (313 nm excitation)). The cis molar ratio reached 35% photostationary state. oxidation to state followed with same led cis-to-trans...

Oxidative addition of (HO)2B−XH3 to M(PH3)2 (X = C, Si, Ge, or Sn; M Pd Pt) was theoretically investigated with MP2-MP4(SDQ) and CCSD(T) methods. easily undergoes oxidative Pt(PH3)2 a moderate activation energy for X C either very small barrier no Sn. Also, (HO)2B−SiH3, (HO)2B−GeH3, (HO)2B−SnH3 undergo Pd(PH3)2 barrier. Only the (HO)2B−CH3 cannot take place, but reductive elimination from Pd(CH3)[B(OH)2](PH3)2 occurs The transition states (TS) these additions are nonplanar except nearly...

A new platinum complex with both an azo-bound dithiolato ligand and azobenzene-bound bipyridine exhibits tristability reversibly controllable using different energy lights.

Abstract Borinium ions, that is, two‐coordinate boron cations, are the most electron‐deficient isolable compounds. As borinium ions have only four formal valence electrons on boron, they should show a strong tendency to accept electron pairs atom fill its shell. Thus chemical reactions of expected give products in which coordination number is increased from two three or four. However, contrary this expectation, we found dimesitylborinium ion (Mes 2 B + ) undergoes twofold 1,2‐carboboration...

A theoretical study of oxidative additions H−CH3, CH3−CH3, H−SiR3, and SiR3−CH3 (RH, Cl, or Me) to Pt(PH3)2 was carried out with ab initio MO/MP2-MP4SDQ, CCD, CCSD methods. The addition reactions C−H Si−H σ-bonds occur through a planar transition state (TS) structure, in accordance the expectation from an orbital interaction diagram. However, CH3−CH3 SiH3−CH3 take place nonplanar TS unexpectedly; dihedral angle δ between PtP2 PtXC planes (X = C Si) is about 70° for X Si 80° C. Intrinsic...

A unique distorted trigonal-bipyramidal geometry observed for the non-heme iron center in protocatechuate 3,4-dioxygenase (3,4-PCD) was carefully examined utilizing a sterically hindered salen complex, which well reproduces endogenous His2Tyr2 donor set with water as an external ligand. X-ray crystal structures of series model complexes containing bis(3,5-dimesitylsalicylidene)-1,2-dimesitylethylenediamine indicate that is achieved upon binding The extent structural change from preferred...

Azobenzene derivatives modified with dithiolato-bipyridine platinum(II) complexes were synthesized, revealing their highly extended photoresponses to the long wavelength region as well unique photocontrollable tristability. The absorptions of trans-1 and trans-2 one azobenzene group on dithiolene bipyridine ligands, respectively, cover range from 300 700 nm. These are ascribed, by means time-dependent (TD)DFT calculations, transitions dithiolene(pi) bipyridine(pi*), namely, interligand...

We recently reported a new one-pot transformation of alkynes into 9,10-diarylphenanthrene derivatives, which proceeds through efficient catalyst-free 1,2-carboboration with 9-chloro-9-borafluorene (1Cl ), yields chlorodibenzoborepin, followed by oxidative deborylation/C-C coupling the resultant chlorodibenzoborepin. Herein, based on experimental observations for using diphenylacetylenes and 1Br or 1OTf as well results from theoretical investigations, we show how substituent boron atom...

A highly twisted CC double bond elicits changes in the physicochemical properties of π-systems.

Abstract We prepared a square cyclic porphyrin dodecamer via the tetramerization of trimer shaped like right angle. The molecule was visualized by scanning tunneling microscopy to be square.

3-, 4-, and 2-ferrocenylazobenzenes, 1, 2, 3, respectively, several derivatives of 1 were synthesized, their photoisomerization behaviors examined. The molecular structures its derivatives, 2-chloro-5-ferrocenylazobenzene (5) 3-ferrocenyl-4'-hydroxylazobenzene (11), determined by X-ray diffraction analysis. 3-Ferrocenyl compound undergoes reversible trans-to-cis isomerization with a single green light source the Fe(III)/Fe(II) redox change. 4- 2-Ferrocenyl compounds, 2 also respond to in...

In this Communication, we report on the development of a ratiometric fluorescent probe for silver(I) ions (AgI) based an arene–metal ion interaction. The selectively senses AgI among various metal with large-emission red shift under aqueous conditions, enabling selective detection AgI. X-ray crystallography and NMR analyses reveal that comes into close contact fluorophore, which induces shift. high sensing selectivity toward might be attributable to restricted rigid conformation cyclic aza...

We synthesized a ladder-shaped 9,9′-bifluorenylidene cyclic dimer (<bold>CBF</bold>), in which the two units are connected directly with covalent bonds.

Abstract Non‐coordinative interactions between a metal ion and the aromatic ring of fluorophore can act as versatile sensing mechanism for detection ions with large emission change fluorophores. We report design fluorescent probes based on arene–metal‐ion their biological applications. This study found that various having different fluorophores binding units displayed significant redshift upon complexation ions, such Ag I , Cd II Hg Pb . X‐ray crystallography complexes confirmed were held in...

Despite continuous and active development of fluorescent metal-ion probes, their molecular design for ratiometric detection is restricted by the limited choice available sensing mechanisms. Here we present a multicolor platform metal ions based on interaction between ion aromatic ring fluorophore (arene-metal-ion, AM, coordination). Our provided probes possessing 1,9-bis(2'-pyridyl)-2,5,8-triazanonane as flexible binding unit attached to tricyclic fluorophore. This architecture allows sense...