Synthesis,Structures, and Optical and Electrochemical Properties of Benzoporphycenes

The first facile syntheses of free‐base di‐ and tetrabenzoporphycenes and their metal complexes are reported, based on retro‐Diels–Alder reactions of the corresponding bicyclo[2.2.2]octadiene‐fused porphycenes, prepared by McMurray coupling of α,α′‐diformyldipyrrole. The photophysical and electrochemical properties are analyzed based on UV/Vis absorption, magnetic circular dichroism (MCD), and fluorescence emission, lifetime and quantum yield measurements, cyclic and differential pulse voltammetry (CV and DPV) and time‐dependent DFT calculations based on B3LYP geometry optimizations. Benzoporphycenes are found to be prime candidates for future use in photodynamic therapy.     

Synthesis and the crystal and electronic structure of Hg4AsI5

New mercury arsenide iodide Hg₄AsI₅ was synthesized and its crystal and electronic structure was determined. The crystal structure is layered. The layers are composed of alternating AsHg₄ tetrahedra and IHg₈ Archimedean antiprisms and are bound by the iodine atoms, which form short Hg-I bonds with all mercury atoms. Band structure calculations provided evidence for very weak interactions between the iodine atoms of the adjacent layers and the ionic character of the iodine atom centering the Archimedean antiprism. Hence, individual [AsHg₄I₄]⁺ clusters and I⁻ anions can be distinguished. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 736–739, May, 2006. Additional details of the crystal structure study (deposition number CSD-416238) can be obtained from the Fachinformationszentrum Karlsruhe, D-76344 Eggenstein-Leopoldshafen, Germany, fax: +(49)7247-808-666; e-mail: crysdata@fiz-karlsruhe.de.     

Syntheses,Structures and Band Gaps of KLnSiS4 （Ln = Sm,Yb）

Two new quaternary sulfides, KSmSiS4 （1） and KYbSiS4 （2）, have been synthesized by high-temperature solid-state reaction. Single,crystal X-ray diffraction analyses indicate that both compounds crystallize in the space group P21/m, and the crystal data are as follows： a = 6.426（11）, b = 6.582（11）, c = 8.602（15）A, β= 107.90（13）°, Z = 2, V= 346.2（10） A^3, Dc = 3.317 g/cm^3, F（000） = 318,μ（MoKα） = 10.334 mm^-1, the final R = 0.0559 and wR = 0.1370 for 1; and α= 6.3244（10）, b = 6.5552（10）, c = 8.5701（15）A, β= 108.001（13）°, Z = 2, V = 337.91（9） A^3, De= 3.621 g/cm^3, F（000） = 334, μ（MoKα） = 15.737 mm^-1, the final R = 0.0422 and wR = 0.0960 for 2. The KLnSiS4 （Ln = Sm, Yb） structure consists of corrugated ∞^2 [LnSiS4]^- layers which are formed by edge-sharing LnS8 bicapped trigonal prisms and SiS4 tetrahedra. The K^＋ cations are located in the cavities defined by S2 anions between the ∞^2[LnSiS4]^- layers. Band-gap analyses show that compounds 1 and 2 are semiconductors with optical band-gaps of 2.40 and 2.34 eV, respectively.     

极性金属间化合物LuSn2的合成、晶体结构及能带特征

在惰性气氛氩气保护下,通过高温固相反应合成得到了一个新的二元极性金属间化合物LuSn2。经X-射线单晶衍射与元素分析等方法确定了其晶体结构。LuSn2属正交晶系,空间群为Cmcm,晶体学参数a=0.435 11(10)nm,b=1.601 6(4)nm,c=0.427 80(8)nm,V=0.298 12(11)nm3,Z=4,R1=0.017 0,wR2=0.032 4。LuSn2属于ZrSi2结构类型,其结构中包含有一维"之"字型Sn链与二维四方格子状Sn层,Lu原子排列在Sn链与Sn层的空隙中。能带结构计算表明LuSn2呈金属导电性。     

Growth, Band Structure and Optical Properties of LiSrBO3 Crystal

The bulk crystal of LiSrBO3 (8.39 g) with a size of 21mm×20mm×15mm was grown by high temperature solution growth method. The relationship between growth habit and crystal structure was discussed. The transmission spectrum shows an UV absorption edge at about 300 nm. The melting temperature of this crystal was determined to be 942 ℃ by DTA-TG measurement. The band structure of the LiSrBO3 crystal was studied by means of the first principle method. An indirect band gap was found to be about 4.0 eV,and a low dielectric constant was estimated to be about 1.9 in terms of theoretical results.     

Synthesis,Band and Crystal Structures,and Optical Properties of the Ternary Compound Mg2Te3O8

The new spiroffite Mg₂Te₃O₈ ( 1 ) was prepared by hydrothemal methods and structurally characterized by single‐crystal X‐ray diffraction analysis. Compound 1 crystallizes in the space group C2/c of the monoclinic system with two formula units in a cell: a = 12.6030(7), b = 5.2254(3), c = 11.6331(7) Å, β = 98.6960(10)°, V = 757.30(8) ų. The structure features a 3D open‐framework with spiroffite topology that has large tunnels approximately 3.2 × 5.5 Å. The optical properties and thermal stability of 1 were characterized by UV and IR spectroscopy as well as TG. Calculations of the electronic band structure along with the density of states (DOS) indicate that the present compound is a semiconductor with an indirect band gap, and that the optical absorption is mainly originated from the charge transitions from O‐2p state to Te‐5p and Te‐5s states.     

Crystal Structure, Energy Band and Optical Properties of Phosphate In（PO3）3

1 INTRODUCTION stand the chemical bonding properties and electronic origins of optical transition for solid In(PO3)3, the During the past decades, many indium phosphates crystal energy band and optical response functions have been reported and researched on their conduc- are also calculated. tivity anisotropy, band structure and optical proper- ties[1, . However, to our current knowledge, the com- 2] 2 EXPERIMENTALAND pounds containing alkaline-earth metals are rarely COMPUTATIO…     

Haloacyl complexes of boron, [(CF3)3BC(O)Hal]- (Hal=F, Cl, Br, I)

The haloacyltris(trifluoromethyl)borate anions [(CF3)3BC(O)Hal]- (Hal=F, Cl, Br, I) have been synthesized by reacting (CF3)3BCO with either MHal (M=K, Cs; Hal=F) in SO2 or MHal (M=[nBu4N]+, [Et4N]+, [Ph4P]+; Hal=Cl, Br, I) in dichloromethane. Metathesis reactions of the fluoroacyl complex with Me3SiHal (Hal=Cl, Br, I) led to the formation of its higher homologues. The thermal stabilities of the haloacyltris(trifluoromethyl)borates decrease from the fluorine to the iodine derivative. The chemical reactivities decrease in the same order as demonstrated by a series of selected reactions. The new [(CF3)3BC(O)Hal]- (Hal=F, Cl, Br) salts are used as starting materials in the syntheses of novel compounds that contain the (CF3)3B-C fragment. All borate anions [(CF3)3BC(O)Hal]- (Hal=F, Cl, Br, I) have been characterized by multinuclear NMR spectroscopy (11B, 13C, 17O, 19F) and vibrational spectroscopy. [PPh4][(CF3)3BC(O)Br] crystallizes in the monoclinic space group P2/c (no. 13) and the bond parameters are compared with those of (CF3)3BCO and K[(CF3)3BC(O)F]. The interpretation of the spectroscopic and structural data are supported by DFT calculations [B3LYP/6-311+G(d)].     

g-CN体系的准粒子能带结构和光学特性

利用多体格林函数理论,本文研究了二维CN体系(包括triazine和tri-s-triazine)的激发态特性。通过GW方法,我们计算了准粒子的能量。考虑电子-空穴相互作用,通过求解Bethe-Salpeter方程,我们获得了激发态能量和光谱。我们发现,在这两种CN体系的价带中,σ轨道和π轨道之间的交换作用非常强烈。由于占据的σ轨道和π轨道之间的准粒子修正量非常不同,因此,为了得到准确的带隙值和光谱,我们需要对这两种轨道开展精确的GW计算。与单层的CN体系相比,双层结构中层与层之间的范德华相互作用使带隙值降低了0.6 eV,而光吸收谱红移了0.2 eV,这是由于双层结构具有更小的激子束缚能。我们计算的吸收峰的位置与实验结果符合很好。实验中的吸收峰主要是由深能级的π轨道到π^*轨道的跃迁形成的。π→π^*跃迁和σ→π^*跃迁之间的耦合能够在长波长范围产生弱的吸收尾巴,如果调整入射光的极化方向,由σ→π^*跃迁产生的高强度的吸收峰将会在更低能量处出现。     

Synthesis and Crystal and Band Structures of YbCu_6In_6 with 3D Framework

A new intermetallic compound,YbCu6In6,has been synthesized by solid-state reaction of the corresponding pure elements in a welded tantalum tube at high temperature.Its crystal structure was established by single-crystal X-ray diffraction.YbCu6In6 crystallizes in tetragonal space group I4/mmm with a = 9.2283(5),c = 5.4015(4),V = 460.00(5) 3,Z = 2,Mr = 1243.20,Dc = 8.976 g/cm3,μ = 38.243 mm-1,F(000) = 1076,and the final R = 0.0258 and wR = 0.0602 for 173 observed reflections with I > 2σ(I).The structure of YbCu6In6 belongs to the ThMn12 type.It is isostructural with RECu6In6(RE = Y,Ce,Pr,Nd,Gd,Tb,Dy),containing one-dimensional(1D) [Cu10In6] cluster chain along the c axis,which is interconnected via sharing the Cu(1) atoms to form a three-dimensional(3D) [Cu6In6] framework with Yb atoms encapsulated in the 1D tunnels along the c axis.Band structure calculations based on Density Functional Theory(DFT) method indicate that YbCu6In6 is metallic.     

Ba2In2Q5 (Q = S,Se): Synthesis,Crystal Structures,Electronic Structures,and Optical Properties

Two ternary metal chalcogenides, Ba₂In₂Q₅ (Q = S, Se) were successfully synthesized by solid‐state reactions. They are isostructural and crystallize in the orthorhombic space group Pbca (no. 61). Both of them have a similar three‐dimensional (3D) framework structure, which is composed of [InQ₄] (Q = S, Se) tetrahedra that are alternatingly connected on layer in the ab plane, with Ba²⁺ cations arranged between In–S or In–Se layers for electric charge balance. The measured Raman and IR spectra show that title compounds have broad transparency range up to 20 μm. From the UV/Vis/NIR diffuse reflectance spectra, it can be seen that the bandgaps of Ba₂In₂S₅ and Ba₂In₂S₅ are 2.47 eV and 2.12 eV, which are larger than these of the calculation values (Ba₂In₂S₅, 2.362 eV and Ba₂In₂Se₅, 1.908 eV), respectively. The calculated partial densities of states indicate that the bandgaps are determined by the interaction of S‐3p and In‐5s (Ba₂In₂S₅) or Se‐4p and In‐5s (Ba₂In₂Se₅), respectively. The calculated birefringences (Δn) are about 0.03 (Ba₂In₂S₅) and 0.05 (Ba₂In₂Se₅) as the wavelength above 1 μm, respectively.     

Lead‐Free Halide Perovskite Nanocrystals: Crystal Structures,Synthesis, Stabilities,and Optical Properties

In recent years, there have been rapid advances in the synthesis of lead halide perovskite nanocrystals (NCs) for use in solar cells, light emitting diodes, lasers, and photodetectors. These compounds have a set of intriguing optical, excitonic, and charge transport properties, including outstanding photoluminescence quantum yield (PLQY) and tunable optical band gap. However, the necessary inclusion of lead, a toxic element, raises a critical concern for future commercial development. To address the toxicity issue, intense recent research effort has been devoted to developing lead‐free halide perovskite (LFHP) NCs. In this Review, we present a comprehensive overview of currently explored LFHP NCs with an emphasis on their crystal structures, synthesis, optical properties, and environmental stabilities (e.g., UV, heat, and moisture resistance). In addition, strategies for enhancing optical properties and stabilities of LFHP NCs as well as the state‐of‐the‐art applications are discussed. With the perspective of their properties and current challenges, we provide an outlook for future directions in this rapidly evolving field to achieve high‐quality LFHP NCs for a broader range of fundamental research and practical applications.     

Syntheses and Crystal Structures of Mononuclear and Binuclear Lanthanide Halide Complexes with Diglyme

Two types of isostructural complexes of lanthanide chlorides with diglyme have been synthesized. These are mononuclear molecular complexes [LnCl₃(diglyme)(THF)] (Ln = Eu ( 1 ), Gd ( 2 ), Dy ( 3 ), Er ( 4 ), Yb ( 5 ); diglyme = diethylen glycol dimethyl ether) and binuclear molecular complexes [LnCl₃(diglyme)]₂ (Ln = Dy ( 3d ), Er ( 4d ), Yb ( 5d )). Complex 1 was obtained by the reaction of [EuCl₃(DME)₂] with diglyme in THF. The complexes 2 – 5 and 3d – 5d resulted from reactions of LnCl₃·6H₂O, (CH₃)₃SiCl and diglyme in THF. The mononuclear complexes 2 – 5 crystallized directly from the solutions where the reactions of lanthanide compounds with diglyme took place. Recrystallizations of the powder products of the same reactions from dichloromethane resulted in the binuclear complexes 3d – 5d . Reactions of lanthanide bromide hydrates, (CH₃)₃SiBr and diglyme in THF achieved mononuclear molecular complexes [LnBr₃(diglyme)(L)] (Ln = Gd, L = H₂O ( 6 ); Ln = Ho, L = THF ( 7 )). Crystals of 6 and 7 were grown by recrystallization from dichloromethane. The lanthanide atoms (Ln = Eu–Yb) are seven‐coordinated in a distorted pentagonal bipyramidal fashion in all reported complexes, 1 – 7 and 3d – 5d . Four oxygen atoms and three halide ions are coordinated to lanthanide atoms in 1 – 7 , [LnX₃(diglyme)(L)]. Four chloride ions, two bridging and two nonbridging, and three oxygen atoms are coordinated to lanthanide atoms in 3d – 5d , [LnCl₃(diglyme)]₂.     

Synthesis and Properties of Mononuclear Group 10 Alkoxy‐Biscarbene Complexes

New Pd ‐ and Pt‐biscarbenes : The synthesis by the stoichiometric transmetalation reactions from Fischer alkoxy‐chromium(0) carbene complexes of stable mononuclear (palladium and platinum) alkoxy‐biscarbene complexes is reported. The structure, bonding situation, and the electronic and redox properties of these complexes are studied by a combination of experimental and computational (DFT) methods.

     

Synthesis, Crystal Structure and Band Structure of EuMg6Sn3.67

EuMg6Sn3.67 has been synthesized by reacting the mixture of the corresponding pure elements at high temperature, and structurally characterized by single-crystal X-ray diffraction study. EuMg6Sn3.67 crystallizes in hexagonal space group P63/m (No. 176) with a = 11.7259(4), c = 4.5507(2), V = 541.88(4)3 , Z = 2, Mr = 734.60, Dc = 4.502 g/cm3 , μ = 14.348 mm-1 , F(000) = 638, the final R = 0.0128 and wR = 0.0378 for 464 observed reflections with Ⅰ > 2σ(Ⅰ). EuMg6Sn3.67 is closely related to the Ba2Mg12Ge7.33 structure type and features a three-dimensional Mg6Sn3.67 framework with one-dimensional hexagonal tunnels along the c-axis occupied by the Eu atoms. Electronic structure calculation indicates that the title compound is metallic.     

Synthesis, Crystal Structure and Band Structure of Sm3In5

A new intermetallic compound, Sm3In5, has been synthesized by solid-state reaction of the corresponding pure elements in a welded niobium tube at high temperature. Its crystal structure was established by single-crystal X-ray diffraction. Sm3In5 crystallizes in orthorhombic, space group Cmcm with a = 10.0137(8), b = 8.1211(7), c = 10.3858(8) , V = 844.60(1) 3, Z = 4, Mr = 1025.15, Dc = 8.062 g/cm3, μ = 33.791 mm-1, F(000) = 1724, the final R = 0.0346 and wR = 0.0775 for 533 observed reflections with I > 2σ(I). The structure of Sm3In5 belongs to the modified Pu3Pd5 type. It is isostructural with La3In5 and β-Y3In5, containing one-dimensional (1D) [In5] cluster chains along the c-axis, which are weakly interconnected via In-In bonds (3.345 ) to form a three-dimensional (3D) structure. The samarium cations are located at the voids between the 1D [In5] cluster chains. Band structure calculations based on Density Function Theory (DFT) method indicate that Sm3In5 is metallic.     

Structures of Trichloromethyl Thiocyanate,CCl3SCN,in Gaseous and Crystalline State

Trichloromethyl thiocyanate, CCl₃SCN, was structurally studied in both the gas and crystal phases by means of gas electron diffraction (GED) and single‐crystal X‐ray diffraction (XRD), respectively. Both experimental studies and quantum chemical calculations indicate a staggered orientation of the CCl₃ group relative to the SCN group. This conclusion is supported by the similarity of the C?SCN bond length to that of the anti‐structure of CH₂ClSCN (Berrueta Martínez et al. Phys. Chem. Chem. Phys. 2015, 17, 15805–15812). 1 Bond lengths and angles are similar for gas and crystal CCl₃SCN structures; however, the crystal structure presents different intermolecular interactions. These include halogen and chalcogen type interactions, the geometry of which was studied. Characteristic C‐Y???N angles (Y=Cl or S) close to 180° provide evidence for typical σ‐hole interactions along the halogen/chalcogen?carbon bond in N???Cl and N???S, intermolecular units.     

Synthesis, Crystal Structure and Chemical Bonding of a New Binary Lu-Sn Phase: Lu11Sn10

A new tetragonal phase of Lu11Sn10 is obtained from high temperature reaction of the pure elements in a welded tantalum tube. Its crystal structure was established by single-crystal X-ray diffraction. Lu11Sn10 crystallizes in the tetragonal space group I4/mmm (No.139) with a=11.2953(18), c=16.424(4), V=2095.5(7)3 , Z=4, Mr=3111.57, Dc=9.863 g/cm3 , μ=62.897 mm-1, F(000)=5124, and the final R=0.0348 and wR=0.0894 for 706 observed reflections with I>2σ(I). The structure of Lu11Sn10 may be derived from the Ho11Ge10 structural type. It is isostructural with Dy11Sn10 , featuring a three-dimensional (3D) framework composed of [Sn4] squares and [Sn2] dimers interlinked via Sn-Sn bonds with two types of one-dimensional (1D) tunnels along the c-axis, which are occupied by isolated Sn atoms, [Sn2] dimers and all the Lu atoms. Band structure calculation based on density functional theory method indicates that Lu11Sn10 is metallic.     

极性金属间化合物MgIn2的合成、晶体结构及能带特征

在惰性气氛氩气保护下,通过高温固相反应合成得到了一个二元极性金属间化合物MgIn2。经X-射线单晶衍射与元素分析等方法确定了其晶体结构。MgIn2属立方体系,空间群为Fd3m(No.227),晶体学参数a=0.956 13(16)nm,V=0.874 1(3)nm3,Z=8,R1=0.035 3,wR2=0.082 8。MgIn2属于CaAl2结构类型,其结构特征为[In4]四面体通过共用顶点In原子链接而成的三维框架结构,Mg原子填充在三维框架的空隙中。能带结构计算表明MgIn2属于金属性的化合物。     

有机晶体材料DAST和DSTMS的电子结构与光学性质

采用基于赝势平面波基组的密度泛函理论(DFT)方法,研究了有机晶体材料4-(4-二甲氨基苯乙烯基)甲基吡啶对甲苯磺酸盐(DAST)和4-(4-二甲氨基苯乙烯基)甲基吡啶2,4,6-三甲基苯磺酸盐(DSTMS)的电子结构和光学性质.结果表明,两种化合物具有相似的能带结构,其中价带顶和导带底分别含有较多二甲氨基和甲基吡啶中N原子的2p轨道成分.在线性光学性质方面,两种化合物具有较高的双折射率(Δn>0.5),在中远红外区均具有较好的透过性能.在二阶非线性光学性质方面,该类晶体具有较强的二阶倍频(SHG)效应,静态倍频系数d11约为150 pm V-1.由能带结构分析结果可知,体系的SHG效应与推拉电子基团之间的电荷转移密切相关,同时乙烯桥键在该电子转移过程中也起着重要作用.