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1.
The ternary indides RE10Ni9+xIn20 (RE = Tb, Dy) were synthesized from the elements by arc‐melting under argon and subsequent annealing. YbNiIn2 was prepared in a sealed tantalum tube in a water‐cooled sample chamber of a high‐frequency furnace. X‐ray powder and single crystal data revealed isotypism with the tetragonal Ho10Ni9In20 type structure, space group P4/nmm for the RE10Ni9+xIn20 compounds: a = 1337.0(2), c = 909.5(2) pm, wR2 = 0.0527, 1795 F2 values, 65 variables for RE = Tb, and a = 1333.63(7), c = 907.2(1) pm, wR2 = 0.0590, 1346 F2 values, 65 variables for RE = Dy. Both indides show an additional nickel site (Ni4) with partial nickel occupancy leading to the refined compositions Tb10Ni9.34(2)In20 and Dy10Ni9.32(2)In20. YbNiIn2 adopts the orthorhombic MgCuAl2‐type structure: Cmcm, a = 430.67(9), b = 1033.0(2), c = 758.1(1) pm, wR2 = 0.0262, 424 F2 values and 16 variable parameters. The crystal chemistry of the RE10Ni9+xIn20 and RENiIn2 compounds is briefly discussed.  相似文献   

2.
The isotypic indides RE4Pt10In21 (RE = La, Ce, Pr, Nd) were prepared by melting mixtures of the elements in an arc‐furnace under an argon atmosphere. Single crystals were synthesized in tantalum ampoules using special temperature modes. The four samples were studied by powder and single crystal X‐ray diffraction: Ho4Ni10Ga21 type, C2/m, a = 2305.8(2), b = 451.27(4), c = 1944.9(2) pm, β = 133.18(7)°, wR2 = 0.045, 2817 F2 values, 107 variables for La4Pt10In21, a = 2301.0(2), b = 448.76(4), c = 1941.6(2) pm, β = 133.050(8)°, wR2 = 0.056, 3099 F2 values, 107 variables for Ce4Pt10In21, a = 2297.4(2), b = 447.4(4), c = 1939.7(2) pm, β = 132.95(1)°, wR2 = 0.059, 3107 F2 values, 107 variables for Pr4Pt10In21, and a = 2294.7(4), b = 446.1(1), c = 1938.7(3) pm, β = 132.883(9)°, wR2 = 0.067, 2775 F2 values, 107 variables for Nd4Pt10In21. The 8j In2 positions of all structures have been refined with a split model. The In1 sites of the lanthanum and the cerium compound show small defects, leading to the refined composition La4Pt10In20.966(6) and Ce4Pt10In20.909(6) for the investigated crystals. The same position shows Pt/In mixing in the praseodymium and neodymium compound leading to the refined compositions Pr4Pt10.084(9)In20.916(9) and Nd4Pt10.050(9)In20.950(9). All platinum atoms have a tricapped trigonal prismatic coordination by rare‐earth metal and indium atoms. The shortest interatomic distances occur for Pt–In followed by In–In. Together, the platinum and indium atoms build up three‐dimensional [Pt10In21] networks in which the rare earth atoms fill distorted pentagonal tubes. The crystal chemistry of RE4Pt10In21 is discussed and compared with the RE4Pd10In21 indides and isotypic gallides.  相似文献   

3.
Mercury(I) chloride reacts with gallium(III) chloride in benzene/1, 2‐dichlorobenzene solution to give the binuclear compound Hg2(GaCl4)2 ( 1 ). Reduction of mercury(I) chloride with mercury in gallium(III) chloride‐benzene mixture leads to the trinuclear compound Hg3(GaCl4)2 ( 2 ). The crystal structures of 1 and 2 were determined by single‐crystal X‐ray diffraction {Hg2(GaCl4)2: triclinic, P1¯, a = 645.21(3), b = 654.44(3), c = 927.17(7) pm, α = 83.526(2)°, β = 74.915(2)°, γ = 61.863(3)°; Hg3(GaCl4)2: monoclinic, P21/c, a = 715.79(1), b = 1501.59(4), c = 1421.43(4) pm, β = 98.9798(9)°}.  相似文献   

4.
The intermetallic compounds CaCuGe, CaAuIn, and CaAuSn can be prepared from the elements in sealed tantalum tubes or in glassy carbon crucibles in a high-frequency furnace. Their crystal structures were determined from single crystal X-ray data. The three compounds crystallize with the same subcell structure (KHg2), however, they form three clearly perceptible superstructures with different unit cells, but all in space groups Pnma: a = 2124.9(6) pm, b = 436.0(2) pm, c = 749.4(5) pm, Z = 12, wR2 = 0.0789, 1303 F2 values, 56 variables for CaCuGe (own structure type), a = 738.2(1) pm, b = 459.4(1) pm, c = 839.4(2) pm, Z = 4, wR2 = 0.0651, 656 F2 values, 20 variables for CaAuIn (TiNiSi type), a = 3690.3(3) pm, b = 470.5(1) pm, c = 813.6(2) pm, Z = 20, wR2 = 0.1294, 1730 F2 values, 92 variables for CaAuSn (new structure type). The three structures may be considered as superstructures of the KHg2 type with an ordered arrangement of the transition metal and germanium (indium, tin) atoms on the mercury position. Each calcium atom in the structures of CaCuGe, CaAuIn, and CaAuSn has an distinctly ordered near-neighbor environment of six transition metal (T) and six p element (X) atoms in the form of two counter-tilted T3X3 hexagons. All known superstructures of the KHg2 type are described in terms of a group-subgroup scheme.  相似文献   

5.
New intermetallic rare earth compounds REAuMg (RE = Y, La–Nd, Sm, Eu, Gd–Yb) were synthesized by reaction of the elements in sealed tantalum tubes in a high‐frequency furnace. The compounds were investigated by X‐ray diffraction both on powders and single crystals. Some structures were refined on the basis of single crystal data. The compounds with Y, La–Nd, Sm, and Gd–Tm adopt the ZrNiAl type structure with space group P62m: a = 770.8(2), c = 419.5(1) pm, wR2 = 0.0269, 261 F2 values for PrAuMg, a = 750.9(2), c = 407.7(1) pm, wR2 = 0.0561, 649 F2 values for HoAuMg with 15 variables for each refinement. Geometrical motifs in HoAuMg are two types of gold centered trigonal prisms: [Au1Mg3Ho6] and [Au2Mg6Ho3]. The gold and magnesium atoms form a three‐dimensional [AuMg] polyanion in which the holmium atoms fill distorted hexagonal channels. The magnesium positions show a small degree of magnesium/gold mixing resulting in the refined compositions PrAu1.012(2)Mg0.988(2) and HoAu1.026(3)Mg0.974(3). EuAuMg and YbAuMg contain divalent europium and ytterbium, respectively. Both compounds crystallize with the TiNiSi type structure, space group Pnma: a = 760.6(3), b = 448.8(2), c = 875.8(2) pm, wR2 = 0.0491, 702 F2 values, 22 variables for EuAuMg, and a = 738.4(1), b = 436.2(1), c = 864.6(2) pm, wR2 = 0.0442, 451 F2 values, and 20 variables for YbAuMg. The europium position shows a small degree of europium/magnesium mixing, and the magnesium site a slight magnesium/gold mixing leading to the refined composition Eu0.962(3)Au1.012(3)Mg1.026(3). No mixed occupancies were found in YbAuMg where all sites are fully occupied. In these structures the europium(ytterbium) and magnesium atoms form zig‐zag chains of egde‐sharing trigonal prisms which are centered by the gold atoms. As is typical for TiNiSi type compounds, also in EuAuMg and YbAuMg a three‐dimensional [AuMg] polyanion occurs in which the europium(ytterbium) atoms are embedded. The degree of distortion of the two polyanions, however, is different.  相似文献   

6.
Two new macrocyclic compounds, [Cu2(L)2](ClO4)4·2CH3OH (1) and [Cu(L)](ClO4)2·2H2O (2) (L = 1,3,10,12,15,18-hexaazatetracyclodocosane) were synthesized by condensation reactions involving amines and formaldehyde in the presence of copper anion. Compound 1 crystallizes in triclinic, space group Pí with a = 10.442(2), b = 14.197(3), c = 17.388(4), α = 91.218(4), β = 90.69(3), γ = 93.756(4)o, V = 2520.4(9)3, Z = 2, F(000) = 1260, Dc = 1.589 Mg/m3, Mr = 1205.92, μ = 1.137 mm-1, λ = 0.71073, the final R = 0.0668 and wR = 0.1573 for 9703 observed reflections with I > 2σ(I). Compound 2 crystallizes in monoclinic, space group C2/c with a = 16.911(2), b = 11.4172(15), c = 27.059(4), β = 107.787(2)o, V = 4974.7(12)3, Z = 8, F(000) = 2504, Dc = 1.610 Mg/m3, Mr = 602.92, μ = 1.155 mm-1, λ = 0.71073 , the final R = 0.0419 and wR = 0.1131 for 4374 observed reflections with I > 2σ(I).  相似文献   

7.
Tetramethyl resorcinarene, which was obtained by acidic condensation of resorcinol with paraacetoaldehyde, was chemically modified to the functionalized O-acyl, O-tosyl and O-acetate derivatives by corresponding acylation, p-toluenesulfonylation and alkylation reactions. The single crystal structures of these functionalized resorcinarenes and the complex of tetramethyl resorcinarene with 2,2'-bipyridine were determined by X-ray diffraction method. All these resorcinarenes adopt the all-cis configuration with four methyl groups stretching to the down rim and form 1D or 2D structures through H-bonds.  相似文献   

8.
Two new organically templated borates, [H2DAB][B7O9(OH)5]·2H2O ( 1 ) and [H2DAB][B7O10(OH)3] ( 2 ), have been synthesized under mild conditions in the presence of DAB acting as structure‐directing agent (DAB = 1,4‐diaminobutane). The structures were determined by single crystal X‐ray diffraction and further characterized by FTIR, elemental analysis, and thermogravimetric analysis. Both 1 and 2 crystallize in the same triclinic system, space group (No. 2); 1: a = 8.238(4) Å, b = 8.348 (5) Å, c = 14.574(8) Å, a = 101.050(3)°, β = 92.313(7)°, γ = 112.694(5)°, V = 900.3(8) Å3, Z = 2; 2: a = 8.8769(3) Å, b = 9.3204(2) Å, c = 10.2204(5) Å, α = 74.474(2)°, β = 85.292(5)°, γ = 72.730(2)°, V = 778.01(5) Å3, Z = 2. The structure of 1 consists of [B7O9(OH)5]2? groups, which represents the first example of organically templated heptaborate. The structure exhibits interesting hydrogen‐bonded network formed by borate polyanion [B14O20(OH)6]4?, which can be regarded as being constructed from the dehydration of the FBBs in 1 . The diprotonated organic amines are filled in the free space of the hydrogen‐bonded network and interact with the inorganic framework by extensive hydrogen bonds.  相似文献   

9.
在甲醇溶液中,将K2NiL·H2O和M(OAC)2(M = Co,Zn)按1:1的摩尔比进行组装反应,得到了镍、钴和镍、锌两种异金属一维链状配位聚合物,其化学组成分别为{[Ni2Co2L2(H2O)2]·CH3OH·3H2O}n(1)和{[Ni2Zn2L2 (H2O)2]·2CH3OH·H2O}n(2),(H4L=2-羟基-3-[(E)-({2-(2-羟基苯甲酰胺基)乙基}亚氨基)甲基]苯甲酸,OAC- = CH3COO-)。通过IR谱,元素分析的方法对其进行了表征,利用X-射线单晶衍射方法对其晶体结构进行了测定,结构分析表明:它们都是由不对称四核单元组成链状配位聚合物。  相似文献   

10.
The present paper covers syntheses and crystal structures of benzyl- and cy-clopentyl-cyclopentadienyl sodium tetrahydrofuranate complexes C6H5CH2C5H4Na·THF (1) and C5H9C5H4Na°THF (2). X-ray diffraction data of the title compounds were collected at a low temperature (about 210K). Structures of both the crystals belong to monoclinic space group P21/n with α=0. 9316(3) nm, b=1. 5161(4) nm, c= 0.9791(3) nm, β=91. 06(3)°Z=4 for (1) and α=1. 6120(7) nm, b=0. 9370(3) nm, c=1. 8475(7) nm, β=109.52(3)°Z = 8 for (2). Both structures were solved by using direct methods and refined by block-matrix least-squares to final values of R = 0. 044 for 520 observed reflections (1) and R = 0. 067 for 921 observed reflections (2). In the crystals the tetrahydrofuranate complexes C6H5CH2C5H4Na·THF and C5H9C5H4Na·THF adopt a puckered chain structure with η5-(C6H5CH2)C5H4 and η5-(C5H9)C5H4 rings connected by a bridge Na (THF) unit.  相似文献   

11.
Two novel compounds 1-(4-fluorobenzyl)-4-chloro-(Z)-3-benzoylhydrazono-2-indolinone(1) and 1-(4-methoxybenzyl)-(Z)-3-benzoylhydrazono-2-indolinone(2) were synthesized and their crystal structures were determined by single-crystal X-ray diffraction.Compound 1(C22H15ClFN3O2) crystallized in the triclinic system,space group P1·with a=0.94198(19) nm,b=1.4339(3) nm,c=1.5018(3) nm,α=101.58(3)°,β=102.96(3)°,γ=102.73°,V=1.8602(6) nm3,Mr=407.82,Dc=1.456 g/cm3,μ=0.240 mm-1,F(000)=840,Z=4,R1=0.0442 and wR2=0.1064.Comp...  相似文献   

12.
New intermetallic rare earth iridium silicides Sm3Ir2Si2, HoIrSi, and YbIrSi were synthesized by reaction of the elements in sealed tantalum tubes in a high‐frequency furnace. The compounds were investigated by X‐ray diffraction both on powders and single crystals. HoIrSi and YbIrSi crystallize in a TiNiSi type structure, space group Pnma: a = 677.1(1), b = 417.37(6), c = 745.1(1) pm, wR2 = 0.0930, 340 F2 values for HoIrSi, and a = 667.2(2), b = 414.16(8), c = 742.8(2) pm, wR2 = 0.0370, 262 F2 values for YbIrSi with 20 parameters for each refinement. The iridium and silicon atoms build a three‐dimensional [IrSi] network in which the holmium(ytterbium) atoms are located in distorted hexagonal channels. Short Ir–Si distances (246–256 pm in YbIrSi) are indicative for strong Ir–Si bonding. Sm3Ir2Si2 crystallizes in a site occupancy variant of the W3CoB3 type: Cmcm, a = 409.69(2), b = 1059.32(7), c = 1327.53(8) pm, wR2 = 0.0995, 383 F2 values and 27 variables. The Ir1, Ir2, and Si atoms occupy the Co, B2, and B1 positions of W3CoB3, leading to eight‐membered Ir4Si4 rings within the puckered two‐dimensional [IrSi] network. The Ir–Si distances range from 245 to 251 pm. The [IrSi] networks are separated by the samarium atoms. Chemical bonding in HoIrSi, YbIrSi, and Sm3Ir2Si2 is briefly discussed.  相似文献   

13.
Two isomers (cis and trans) of [Nb6Cl9O3(NCS)6]5– niobium cluster complexes characterized by an ordered arrangement of oxygen and chlorine ligands over the 12 inner positions in the cluster core were prepared by reaction of Cs2LaNb6Cl15O3 and ScNb6Cl13O3 solid state compounds with aqueous solution of potassium thiocyanate. The cis and trans isomers (idealized C 2 v and D 3 symmetry, respectively) crystallize with counter cations and water molecules to form the following salts: Cs4.75K0.25[Nb6Cl9O3(NCS)6] · 5.5H2O (1) and Cs2.5K2.5[Nb6Cl9O3(NCS)6] · 2H2O (2), respectively. The trans isomer is ordered in structure 1 (s.g.: C2/c), while in the structure of 2 (s.g.: Pnma), the cis isomer is randomly disordered over two positions that correspond one to each other by a mirror plane. Interestingly, the treatment of thiocyanato complexes cis and trans with hydrochloric acid led to substitution of (NCS) ligands by Cl and to formation of soluble complexes [Nb6Cl9O3Cl6]5–. The cesium salt of trans-[Nb6Cl9O3Cl6]5– was crystallized as Cs5[Nb6Cl15O3] · CsCl · 7H2O (3) and structurally characterized. Indeed, the formation of soluble [Nb6Cl9O3(NCS)6]5– intermediates is a necessary step towards the formation of soluble anions.  相似文献   

14.
Reactions of [LnCl3(DME)2] (Ln = Nd, Sm, Ho, Lu; DME = dimethoxyethane) and diglyme (diglyme = diethylen glycol dimethyl ether) in THF resulted in polymeric [LnCl3(diglyme)]n (Ln = Nd ( 1 ), Sm ( 2 )) or mononuclear complexes [LnCl3(diglyme)(THF)] (Ln = Ho ( 3 ), Lu ( 4 )). Neodymium and samarium atoms in 1 and 2 are eight‐coordinated by three oxygen atoms from diglyme, one terminal and four bridging chloride ions. Holmium and lutetium atoms in 3 and 4 are seven‐coordinated by three oxygen atoms from diglyme, three chloride ions and one oxygen atom from THF. [ErCl3(diglyme)(H2O)] ( 5 ) resulted from the reaction of ErCl3·6H2O, (CH3)3SiCl and diglyme in THF. The molecular structures of 3 , 4 and 5 are similar, with either a molecule of THF coordinated to the lanthanide atom in 3 and 4 or with a molecule of water coordinated in 5 .  相似文献   

15.
Two coordination polymers, namely, {[Zn(bpea) (bmp)] · H2O}n ( 1 ) and {[Ni(bpea)(bimb)] · DMF}n ( 2 ) [H2bpea = biphenylethene‐4,4′‐dicarboxylate, bmp = 1,4‐bis(2‐methylimidazol‐3‐ium‐1‐yl)biphenyl and bimb = 1,4‐bis(1‐imidazol‐yl)‐2,5‐dimethyl benzene], were synthesized under solvothermal conditions with mixed organic ligands. Single crystal X‐ray diffraction reveals that complex 1 features a three‐dimensional (3D) structure with a sixfold interpenetrating dia net. Complex 2 shows a 3D fivefold interpenetrating dia topology. Furthermore, the solid state luminescent properties of complexes 1 and 2 were investigated at room temperature.  相似文献   

16.
The rare earth-nickel-indides RE14Ni3In3 (RE=Sc, Y, Gd-Tm, Lu) were synthesized from the elements by arc-melting and subsequent annealing. The compounds were investigated on the basis of X-ray powder and single crystal data: Lu14Co2In3 type, P42/nmc, Z=4, a=888.1(1), c=2134.7(4), wR2=0.0653, 1381 F2 values, 63 variables for Sc13.89Ni3.66In2.45; a=961.2(1), c=2316.2(5), wR2=0.0633, 1741 F2 values, 64 variables for Y13.84Ni3.19In2.97; a=965.3(1), c=2330.5(5), wR2=0.0620, 1765 F2 values, 63 variables for Gd14Ni3.29In2.71; a=956.8(1), c=2298.4(5), wR2=0.0829, 1707 F2 values, 64 variables for Tb13.82Ni3.36In2.82; a=951.7(1), c=2289.0(5), wR2=0.0838, 1794 F2 values, 64 variables for Dy13.60Ni3.34In3.06; a=948.53(7), c=2270.6(1), wR2=0.1137, 1191 F2 values, 64 variables for Ho13.35Ni3.17In3.48; a=943.5(1), c=2269.1(5), wR2=0.0552, 1646 F2 values, 64 variables for Er13.53Ni3.14In3.33; a=938.42(7), c=2250.8(1), wR2=0.1051, 1611 F2 values, 64 variables for Tm13.47Ni3.28In3.25; a=937.3(1), c=2249.6(5), wR2=0.0692, 1604 F2 values, 64 variables for Tm13.80Ni3.49In2.71; and a=933.4(1), c=2263.0(5), wR2=0.0709, 1603 F2 values, 64 variables for Lu13.94Ni3.07In2.99. The RE14Ni3In3 indides show significant Ni/In mixing on the 4c In1 site. Except the gadolinium compound, the RE14Ni3In3 intermetallics also reveal RE/In mixing on the 4c RE1 site, leading to the refined compositions. Due to the high rare earth metal content, the seven crystallographically independent RE sites have between 9 and 10 nearest RE neighbors. The RE14Ni3In3 structures can be described as a complex intergrowth of rare earth-based polyhedra. Both nickel sites have a distorted trigonal-prismatic rare earth coordination. An interesting feature is the In2-In2 dumb-bell at an In2-In2 distance of 304 pm (for Gd14Ni3.29In2.71). The crystal chemical peculiarities of the RE14Ni3In3 indides are briefly discussed.  相似文献   

17.
Three open‐framework gallium phosphates [C6H16N2][Ga(HPO4)(PO4)] ( 1 ), {H[C6H16N2]2[Ga7(OH)2(PO4)8]} ( 2 ), and {H[C4H12N2]2[Ga7(OH)2(PO4)8] · 2H2O} ( 3 ) were solvothermally synthesized in the presence of 2,6‐dimethylpyrazine, N‐ethylpiperazine, and piperazine as templates, respectively. Compound 1 possesses an infinite one‐dimensional chain structure connected by hydrogen‐bond interactions to generate a 3D supramolecular framework. Compounds 2 and 3 show similar inorganic framework structures, which may be viewed as the assembly of a secondary building unit (SBU), Ga6P8 containing two GaO4, two GaO5, two GaO6 as well as eight PO4 groups. The SBUs are linked with each other by vertex‐sharing oxygen atoms to form 2D sheets, which are further connected by GaO4 tetrahedra to result in the final 3D open‐framework with left‐ and right‐handed helical chains. In these materials, the well‐ordered organic species reside in the voids of structures and interact with the framework by way of hydrogen bonds.  相似文献   

18.
ZnII and CdII coordination polymers with dicarboxylate and imidazole‐containing ligands, namely, [Cd (2,3‐PDC)(L)]n ( 1 ) and {[Zn(3,4‐PDC) (L)0.5] · H2O}n ( 2 ), [2,3‐H2PDC = 2,3‐pyridine dicarboxylate, 3,4‐H2PDC = 3,4‐pyridine dicarboxylate, and L = 1,4‐bis(2‐methylimidazol‐3‐ium‐1‐yl)biphenyl], were prepared and characterized by elemental analysis, IR spectroscopy, and X‐ray diffraction. Complex 1 shows a three‐dimensional (3D) structure with threefold interpenetrating diamond topology. Complex 2 features a 3D framework with twofold interpenetrating dmc topology. Moreover, the luminescent properties of complexes 1 and 2 were also investigated.  相似文献   

19.
The rare earth-platinum-indides Nd6Pt13In22, Sm6Pt12.30In22.70, and Gd6Pt12.48In22.52 were synthesized from the elements by arc-melting of the components. Single crystals were grown using special annealing sequences. The three indides were investigated by X-ray powder and single crystal diffraction: Tb6Pt12In23 type, C2/m, Z=2, a=2811.9(6), b=441.60(9), , β=112.10(3)°, wR2=0.0629, 3645 F2 values, 126 variables for Nd6Pt13In22, a=2821.9(6), b=443.06(9), , β=112.39(3)°, wR2=0.0543, 3679 F2 values, 127 variables for Sm6Pt12.30In22.70, and a=2818.5(6), b=439.90(9), , β=112.29(3)°, wR2=0.0778, 3938 F2 values, 127 variables for Gd6Pt12.48In22.52. Most platinum atoms in these structures have a distorted trigonal prismatic coordination by rare earth metal and indium atoms. Together, the platinum and indium atoms build up a complex three-dimensional [Pt12+xIn23−x] polyanionic network in which the rare earth metal atoms fill distorted pentagonal and hexagonal channels. The 2c Wyckoff site in these structures plays a peculiar role. This site is occupied by indium in the prototype Tb6Pt12In23, while platinum atoms fill the 2c site in Nd6Pt13In22, leading to a linear Pt3 chain with Pt-Pt distances of 275 pm. The crystals with samarium and gadolinium as rare earth metal component show mixed Pt/In occupancies.  相似文献   

20.
Three bis‐acylamide compounds, N1,N4‐bis(pyridin‐4‐yl)‐cyclohexane‐1, 4‐dicarboxamide ( L1 ), 1, 1′‐(1, 3‐phenylenedicarbonyl‐)bis(1H‐1, 2, 3‐benzotriazole) ( L2 ), and N1,N4‐bis(1H‐1, 2, 4‐triazole) phthalamide ( L3 ) were synthesized. L1 , L2 , and a CuII complex based on L3 formulated as CuCl2( L3 )2(en)2 ( 1 ) (en = ethylenediamine) were structurally characterized by single‐crystal X‐ray diffraction for the first time. L1 , L2 , and L3 exhibit different photoluminescence properties.  相似文献   

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