The Absorption Spectrum of the Lowest Triplet State in Crystalline trans-Stilbene

The absorption spectrum of the lowest triplet state (T₁*-S₀) of trans-stilbene is observed between 14,000 and 18,000 cm^?1 with a crystal four centimeters long, cooled to 4.2°.K. This transition is more intense (f=3×10^?9) than the similar transition in anthracene, due to vibration-induced spin-orbital coupling. Vibrational structures in the spectrum are well resolved and seven frequencies are assigned to normal modes in the T₁* state of trans-stilbene. Exciton structures in crystal are not resolved.     

高纯度可溶性单壁碳纳米管的吸收光谱

经过K₂S₂O₈的稀硫酸溶液氧化处理的粗制单壁碳纳米管样品, 在水、DMF 和乙醇等极性溶剂中具有非常好的溶解性. 通过在DMF介质中多次进行超声波分散和高速离心分离, 成功地获得了高纯度可溶性的单壁碳纳米管. UV-vis-NIR吸收光谱研究表明, 这种高纯度可溶性的单壁碳纳米管呈现出更多的吸收特征和更高的吸收强度. 进一步的研究表明, 单壁碳纳米管的纯度达到了“参比样品”的160%, 其单根分散度达到5%以上.     

Phosphorus‐Stabilized Titanium Carbene Complexes: Synthesis,Reactivity and DFT Studies

The synthesis of two novel titanium carbene complexes from the bis(thiophosphinoyl)methanediide geminal dianion 1 (SCS^2?) is described. Dianion 1 reacts cleanly with 0.5 equivalents of [TiCl₄(thf)₂] to afford the bis‐carbene complex [(SCS)₂Ti] ( 2 ) in 86 % yield. The mono‐carbene complex [(SCS)TiCl₂(thf)] ( 3 ) can also be obtained by using an excess of [TiCl₄(thf)₂]. The structures of 2 and 3 are confirmed by X‐ray crystallography. A strong nucleophilic reactivity towards various electrophiles (ketones and aldehydes) is observed. The reaction of 3 with N,N′‐dicyclohexylcarbodiimide (DCC) and phenyl isocyanate leads to the formation of two novel diphosphinoketenimines 8 a and 8 b . The bis‐titanium guanidinate complex 9 is trapped as the by‐product of the reaction with DCC. The X‐ray crystal structures of 8 a and 9 are presented. The mechanism of the reaction between complex 3 and DCC is rationalized by DFT studies.     

Synthesis,Characterization, and Reactivity of a Uranium(VI) Carbene Imido Oxo Complex

We report the uranium(VI) carbene imido oxo complex [U(BIPM^TMS)(NMes)(O)(DMAP)₂] ( 5 , BIPM^TMS=C(PPh₂NSiMe₃)₂; Mes=2,4,6‐Me₃C₆H₂; DMAP=4‐(dimethylamino)pyridine) which exhibits the unprecedented arrangement of three formal multiply bonded ligands to one metal center where the coordinated heteroatoms derive from different element groups. This complex was prepared by incorporation of carbene, imido, and then oxo groups at the uranium center by salt elimination, protonolysis, and two‐electron oxidation, respectively. The oxo and imido groups adopt axial positions in a T‐shaped motif with respect to the carbene, which is consistent with an inverse trans‐influence. Complex 5 reacts with tert‐butylisocyanate at the imido rather than carbene group to afford the uranyl(VI) carbene complex [U(BIPM^TMS)(O)₂(DMAP)₂] ( 6 ).     

Synthesis,Characterization, and Reactivity of a Uranium(VI) Carbene Imido Oxo Complex

We report the uranium(VI) carbene imido oxo complex [U(BIPM^TMS)(NMes)(O)(DMAP)₂] ( 5 , BIPM^TMS=C(PPh₂NSiMe₃)₂; Mes=2,4,6‐Me₃C₆H₂; DMAP=4‐(dimethylamino)pyridine) which exhibits the unprecedented arrangement of three formal multiply bonded ligands to one metal center where the coordinated heteroatoms derive from different element groups. This complex was prepared by incorporation of carbene, imido, and then oxo groups at the uranium center by salt elimination, protonolysis, and two‐electron oxidation, respectively. The oxo and imido groups adopt axial positions in a T‐shaped motif with respect to the carbene, which is consistent with an inverse trans‐influence. Complex 5 reacts with tert‐butylisocyanate at the imido rather than carbene group to afford the uranyl(VI) carbene complex [U(BIPM^TMS)(O)₂(DMAP)₂] ( 6 ).     

Stable Radical Cation and Dication of an N‐Heterocyclic Carbene Stabilized Digallene: Synthesis,Characterization and Reactivity

One‐ and two‐electron oxidation of a digallene stabilized by an N‐heterocyclic carbene afforded the first stable gallium‐based radical cation and dication salts, respectively. Structural analysis and theoretical calculations reveal that the oxidation occurs at the Ga=Ga double bond, leading to removal of π electrons of the double bond and a decrease of the bond order. The spin density of the radical cation mainly locates at the two gallium centers as demonstrated by EPR spectroscopy and theoretical calculations. Moreover, the reactivity of the radical cation salt toward nBu₃SnH and cyclo‐S₈ was studied; a digallium–hydride cation salt containing a Ga?Ga single bond and a gallium sulfide cluster bearing an unprecedented ladder‐like Ga₄S₄ core structure were obtained, respectively.     

A Cationic Zinc Hydride Cluster Stabilized by an N‐Heterocyclic Carbene: Synthesis,Reactivity, and Hydrosilylation Catalysis

The trinuclear cationic zinc hydride cluster [(IMes)₃Zn₃H₄(THF)](BPh₄)₂ ( 1 ) was obtained either by protonation of the neutral zinc dihydride [(IMes)ZnH₂]₂ with a Brønsted acid or by addition of the putative zinc dication [(IMes)Zn(THF)]²⁺. A triply bridged thiophenolato complex 2 was formed upon oxidation of 1 with PhS? SPh. Protonolysis of 1 by methanol or water gave the corresponding trinuclear dicationic derivatives. At ambient temperature, 1 catalyzed the hydrosilylation of aldehydes, ketones, and nitriles. Carbon dioxide was also hydrosilylated under forcing conditions when using (EtO)₃SiH, giving silylformate as the main product.     

Stable Radical Cation and Dication of an N-Heterocyclic Carbene Stabilized Digallene: Synthesis,Characterization and Reactivity

One- and two-electron oxidation of a digallene stabilized by an N-heterocyclic carbene afforded the first stable gallium-based radical cation and dication salts, respectively. Structural analysis and theoretical calculations reveal that the oxidation occurs at the Ga=Ga double bond, leading to removal of π electrons of the double bond and a decrease of the bond order. The spin density of the radical cation mainly locates at the two gallium centers as demonstrated by EPR spectroscopy and theoretical calculations. Moreover, the reactivity of the radical cation salt toward nBu₃SnH and cyclo-S₈ was studied; a digallium–hydride cation salt containing a Ga−Ga single bond and a gallium sulfide cluster bearing an unprecedented ladder-like Ga₄S₄ core structure were obtained, respectively.     

Electronic Absorption Spectra of Planar,Conjugated Biradicals in the Lowest Triplet State

The semiempirical PPP-SCF-SCI method has been adapted to even-electron, open-shell π-systems by performing the SCF calculation on the lowest triplet configuration and choosing a limited set of single electronic excitations from the latter for configuration interaction. The basic approximations and parameters of the standard PPP model were retained. The results were compared with experimental triplet-triplet absorption spectra of aromatic hydrocarbons and with more elaborate calculations available for selected systems. The reliability of the model was found to be comparable to its well-known performance in predicting the absorption spectra of closed-shell π-systems and of conjugated radicals. Triplet-state absorption spectra for various planar, conjugated biradicals were calculated and, where possible, compared with experimental data.     

The EPR Spectrum of Triplet Mesitylphosphinidene: Reassignment and New Assignment

Low‐temperature UV‐photolysis of mesitylphosphiranes under highly anaerobic conditions leads to the formation of the triplet mesitylphosphinidene (MesP). The recorded X‐band EPR spectrum of triplet MesP and the derived zero‐field splitting parameter D =4.116 cm⁻¹ differ significantly from those reported previously for this intermediate. New magnetic parameters of mesitylphosphinidene are discussed along with the results of DFT calculations.     

Visible‐Light Photoactive,Highly Efficient Triplet Sensitizers Based on Iodinated Aza‐BODIPYs: Synthesis,Photophysics and Redox Properties

A series of novel iodinated NO₂‐substituted aza‐BODIPYs have been synthesized and characterized. Highly desirable photophysical and photochemical properties were induced in NO₂‐substituted aza‐BODIPYs by iodination of the pyrrole rings. In particular, high values of singlet oxygen quantum yields (Φ_Δ) ranging from 0.79 to 0.85 were measured. The photooxygenation process proceeds via a Type II mechanism under the experimental conditions applied. The compounds studied exhibited an absorption band within the so‐called “therapeutic window”, with λ_max located between 645 nm to 672 nm. They were non‐fluorescent at room temperature with excited singlet‐state lifetimes within the picosecond range as measured by femtosecond transient absorption. Nanosecond laser flash photolysis experiments revealed T₁→T_n absorption spanning from ca. 400 nm to ca. 500 nm and allowed determination of the triplet‐state lifetimes. The estimated triplet lifetimes (τ_T) in deaerated acetonitrile ranged between 2.74 μs and 3.50 μs. As estimated by CV/DPV measurements, all iodinated aza‐BODIPYs studied exhibited one irreversible oxidation and two quasi‐reversible reductions processes. Estimation of the E_HOMO gave the value of ?6.06 to ?6.26 eV while the E_LUMO was found to be located at ca. ?4.6 eV. Thermogravimetric (TGA) analysis revealed that iodinated aza‐BODIPYs were stable up to approximately 300 °C. All compounds studied exhibit high photostability in toluene solution.     

Planar N‐Heterocyclic Carbene Diarylborenium Ions: Synthesis by Cationic Borylation and Reactivity with Lewis Bases

The NHC–borane adduct (IBn)BH₃ ( 1 ) (NHC= N‐heterocyclic carbene; IBn=1,3‐dibenzylimidazol‐2ylidene) reacts with [Ph₃C][B(C₆F₅)₄] through sequential hydride abstraction and dehydrogenative cationic borylation(s) to give singly or doubly ring closed NHC–borenium salts 2 and 3 . The planar doubly ring closed product [C₃H₂(NCH₂C₆H₄)₂B][B(C₆F₅)₄] is resistant to quaternization at boron by Et₂O coordination, but forms classical Lewis acid–base adducts with the stronger donors Ph₃P, Et₃PO, or 1,4‐diazabicyclo[2.2.2]octane (DABCO). Treatment of 3 with tBu₃P selectively yields the unusual oligomeric borenium salt trans‐[(C₃H₂(NCH₂C₆H₄)₂B)₂(C₃H₂(NCHC₆H₄)₂B)][B(C₆F₅)₄] ( 7 ).     

Molecular Design of Highly Efficient Heavy‐Atom‐Free Triplet BODIPY Derivatives for Photodynamic Therapy and Bioimaging

Novel BODIPY photosensitizers were developed for imaging‐guided photodynamic therapy. The introduction of a strong electron donor to the BODIPY core through a phenyl linker combined with the twisted arrangement between the donor and the BODIPY acceptor is essential for reducing the energy gap between the lowest singlet excited state and the lowest triplet state (ΔE_ST), leading to a significant enhancement in the intersystem crossing (ISC) of the BODIPYs. Remarkably, the BDP‐5 with the smallest ΔE_ST (ca. 0.44 eV) exhibited excellent singlet oxygen generation capabilities in both organic and aqueous solutions. BDP‐5 also displayed bright emission in the far‐red/near‐infrared region in the condensed states. More importantly, both in vitro and in vivo studies demonstrated that BDP‐5 NPs displayed a high potential for photodynamic cancer therapy and bioimaging.