Abstract Recently, luminophores showing efficient room‐temperature phosphorescence (RTP) have gained tremendous interest due to their numerous applications. However, most phosphors are derived from transition metal complexes because of intrinsic fast intersystem crossing (ISC) induced by strong spin–orbit coupling (SOC) constants the heavy metal. Metal‐free RTP materials rare and become a promising field they inexpensive environmentally friendly. This review summarizes organic molecular with...

Abstract The push–pull character of a series donor–bithienyl–acceptor compounds has been tuned by adopting triphenylamine or 1,1,7,7‐tetramethyljulolidine as donor and B(2,6‐Me 2 ‐4‐RC 6 H ) (R=Me, C F 5 3,5‐(CF 3 B[2,4,6‐(CF ] an acceptor. Ir‐catalyzed CH borylation was utilized in the derivatization boryl acceptors tetramethyljulolidine donor. acceptor strengths were evaluated electrochemical photophysical measurements. In solution, compound with strongest acceptor, ((FMes) B), strongly...

R–Ph–B(FMes)₂compounds exhibit low reduction potentials, bright emission, a TICT state and unusual long-lived phosphorescence at temperature.

This case study on a series of monomeric, dimeric and polymeric Cu(I) chlorido NHC-picolyl complexes shows that cuprophilic interactions can ensure strong spin-orbit coupling for fast (reverse)intersystem-crossing T1 ↔ S1 → S0, therefore serve as design motif the construction highly efficient Cu(I)-based TADF or emitters.

Abstract Achieving highly efficient phosphorescence in purely organic luminophors at room temperature remains a major challenge due to slow intersystem crossing (ISC) rates combination with effective non‐radiative processes those systems. Most phosphorescent (RTP) materials have O‐ or N‐lone pairs leading low lying (n, π*) and (π, excited states which accelerate k isc through El‐Sayed's rule. Herein, we report the first persistent RTP lifetimes up 0.5 s from simple triarylboranes no lone...

Abstract The investigation of the mechanisms mechanochromic luminescence is fundamental importance for development materials photonic sensors, data storage, and switches. structural origin this phenomenon in phosphorescent molecular systems rarely known thus formulation structure–property relationships remains challenging. Changes M–M interactions have been proposed as main mechanism with d 10 coinage metal compounds. Herein, we describe a new mechanism—a mechanically induced reversible...

A series of tetracationic quadrupolar chromophores containing three-coordinate boron π-acceptors linked by different π-bridges, namely 4,4'-biphenyl, 2,7-pyrene, 2,7-fluorene, 3,6-carbazole and 5,5'-di(thien-2-yl)-3,6-diketopyrrolopyrrole, were synthesized. While their neutral precursors 1-5 displayed highly solvatochromic fluorescence, the water-soluble target molecules 1M-5M, did not, but emission colour could be tuned from blue to pink changing π-bridge. Compound 5M, diketopyrrolopyrrole...

Abstract A series of 12 dinuclear complexes [Ln 2 Cl 6 (μ‐4,4′‐bipy)(py) ], Ln=Y, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, ( 1 – , respectively) was synthesized by an anhydrous solvothermal reaction in pyridine. The contain a 4,4′‐bipyridine bridge and exhibit coordination sphere closely related to luminescent lanthanide MOFs based on LnCl 3 4,4‐bipyridine. therefore function as molecular model system provide better understanding the luminescence mechanisms Ln‐N‐MOFs (4,4′‐bipy) ] ⋅...

The rare case of a metal-triggered broad-band yellow emitter among inorganic-organic hybrid materials was achieved by in situ codoping the novel imidazolate metal-organic framework ∞(3)[Ba(Im)2] with divalent europium. emission maximum this dense is center gap primary light-emitting diode phosphors. Up to 20% Eu2+ can be added replace Ba2+ as connectivity centers without causing observable phase segregation. High-resolution energy-dispersive X-ray spectroscopy showed that incorporation even...

A highly selective and general photoinduced C-Cl borylation protocol that employs [Ni(IMes)2] (IMes = 1,3-dimesitylimidazoline-2-ylidene) for the radical of chloroarenes is reported. This system operates with visible light (400 nm) achieves a wide range B2pin2 at room temperature in excellent yields high selectivity, thereby demonstrating its broad utility functional group tolerance. Mechanistic investigations suggest reactions proceed via process. EPR studies demonstrate undergoes very fast...

The importance of relativity and dispersion in metallophilicity has been discussed numerous studies. existence hybridization the bonding between closed shell d10-d10 metal atoms also speculated, but presence attractive MO interaction metal-metal bond is still a matter an ongoing debate. In this comparative study, quantitative molecular orbital analysis energy decomposition carried out on metallophilic atomic dimers (M+···M+) perpendicular [H3P-M-X]2 (where M = Cu, Ag, Au; X F, Cl, Br, I)....

Abstract In this combined experimental and theoretical study, a computational protocol is reported to predict the excited states in D‐π‐A compounds containing B( F Xyl) 2 ( Xyl = 2,6‐bis(trifluoromethyl)phenyl) acceptor group for design of new thermally activated delayed fluorescence (TADF) emitters. To end, effect different donor π‐bridge moieties on energy gaps between local charge‐transfer singlet triplet examined. prove computationally aided concept, D‐π‐B( 1 – 5 were synthesized fully...

Reversible conversion between excited-states is key to many photophysical phenomena. We studied the equilibrium LE and CT states by time-resolved temperature-dependent fluorescence, fs- ns-transient absorption, LR-TDDFT calculations.

A hitherto unprecedented polynuclear phosphinine-Cu(I) complex has been prepared and crystallographically characterized. The molecular structure in the crystal verifies presence of heterocubane-type tetrameric cluster [LCuBr]4 (L = 2,4-diphenyl-5-methyl-6-(2,3-dimethylphenyl)phosphinine), which unexpectedly shows solid state temperature-independent orange phosphorescence solely from an (3)XMLCT state, clear contrast to well-established dual-emissive-state model for luminescent Cu4X4L4 clusters.

We have synthesized a series of luminescent trigonal [CuX(dtbphen)] (X = I (), Br Cl CN dtbphen 2,9-di-tert-butylphenanthroline) and tetrahedral [Cu2(μ-I)2(L)2] (L phenanthroline 2,9-dimethylphenanthroline ()) copper diimine complexes. Bearing in mind the chemical simplicity this class long-known Cu(i) compounds, it is surprising that they exhibit non-trivial photophysical properties, which not been fully recognized. They display broad XMLCT absorption between ca. 450-600 nm, emission...

Via regioselective Ir-catalyzed C-H borylation and subsequent reactions (i.e., via Br4-Per or (BF3K)4-Per intermediates), we have introduced strong π-donors acceptors at the 2,5,8,11-positions of perylene leading to unusual properties. Thus, incorporation four donor diphenylamine (DPA) acceptor Bmes2 (mes = 2,4,6-Me3C6H2) moieties yields novel compounds which can be reversibly oxidized reduced times, respectively, an unprecedented behavior for monomeric derivatives. Spectroelectrochemical...

Abstract Achieving highly efficient phosphorescence in purely organic luminophors at room temperature remains a major challenge due to slow intersystem crossing (ISC) rates combination with effective non‐radiative processes those systems. Most phosphorescent (RTP) materials have O‐ or N‐lone pairs leading low lying (n, π*) and (π, excited states which accelerate k isc through El‐Sayed's rule. Herein, we report the first persistent RTP lifetimes up 0.5 s from simple triarylboranes no lone...

A series of 12 lanthanide coordination polymers was synthesized from anhydrous LnCl3 and 1,2-di(4-pyridyl)ethylene (dpe) under solvothermal conditions in either thiazole (thz) or pyridine (py). The reactions yielded ∞1[Ln2Cl6(dpe)2(thz)4]·dpe with Ln = Ce (1), Nd (2), ∞1[LnCl3 (dpe)(py)2]·(dpe/py) Gd (3), Er (4), ∞1[LnCl3(dpe) (thz)2](dpe/thz) Sm (5), (6), Tb (7), Dy (8), (9), Yb (10), as well ∞1[HoCl3(dpe)(thz)2]·thz (11) ∞2[La2Cl6(dpe)3(py)2]·dpe (12). One-dimensional (CPs) a...

Abstract Using 4‐phenylpyridine or 2‐phenylpyridine in place of biphenyl, two electron‐poor phenylpyridyl‐fused boroles, [TipPBB1] 4 and TipPBB2 were prepared. adopts a unique coordination mode forms tetramer with cavity both the solid state solution. The boron center is 4‐coordinate but system dissociates solution, leading to 3‐coordinate borole species. Compared its borafluorene analogues, electron‐accepting ability largely enhanced by pyridyl group. exhibits dual fluorescence solution due...

A study on the reactivity of N-heterocyclic silylene Dipp2 NHSi (1,3-bis(diisopropylphenyl)-1,3-diaza-2-silacyclopent-4-en-2-yliden) with transition metal complexes [Ni(CO)4 ], [M(CO)6 ] (M=Cr, Mo, W), [Mn(CO)5 (Br)] and [(η5 -C5 H5 )Fe(CO)2 (I)] is reported. We demonstrate that silylenes, higher homologues now ubiquitous NHC ligands, show a remarkably different behavior in coordination chemistry compared to ligands. Calculations electronic features these ligands revealed significant...

A three color white light emitting MOF with temperature and dopant dependent chromaticity is achieved by in situ co-doping of IFP-1 lanthanide ions.

A water-soluble tetracationic quadrupolar bis-triarylborane chromophore showed strong binding to ds-DNA, ds-RNA, ss-RNA, as well the naturally most abundant protein, BSA. The novel dye can distinguish between DNA/RNA and BSA by fluorescence emission separated Δ ν˜ =3600 cm-1 , allowing for simultaneous quantification of protein (BSA) in a mixture. applicability such fluorimetric differentiation vitro was demonstrated, strongly supporting protein-like target dominant site 1 cells. Moreover,...

Experimental and theoretical investigations on the novel 14 VE complexes [M⁰(iPr₂Im)₂] (M = Pd<bold>3</bold>, Pt<bold>4</bold>; iPr₂Im 1,3-di-isopropyl-imidazolin-2-ylidene) a comparison to their Ni congener reveal that NHC–M–NHC angle bending is key understand reactivity of d¹⁰-[M(NHC)₂] complexes.

Abstract The synthesis and characterization of 10‐(dimesitylboryl)‐ N , ‐di‐ p ‐tolylbenzo[ c ]phenanthren‐4‐amine (3‐B(Mes) 2 ‐[4]helix‐9‐N( ‐Tol) 1 ) 13‐(dimesitylboryl)‐ ‐tolyldibenzo[ g ]phenanthren‐8‐amine ‐[5]helix‐12‐N( are reported herein. Their electrochemical photophysical properties have been studied experimentally theoretically. donor acceptor‐substituted helicene derivatives exhibit moderate fluorescence quantum yields in THF ( Φ f =0.48 0.61 for respectively), which higher than...

Two N-methylpyridinium compounds and analogous N-protonated salts of 2- 2,7-substituted 4-pyridyl-pyrene were synthesised their crystal structures, photophysical properties both in solution the solid state, electrochemical spectroelectrochemical studied. Upon methylation or protonation, emission maxima are significantly bathochromically shifted compared to neutral compounds, although absorption remain almost unchanged. As a result, cationic show very large apparent Stokes shifts up 7200 cm-1...