Crystal structure, luminescent and thermochromic properties of bis-1,10-phenan-throlinium hexachlorotellurate(IV) dihydrate

Abstract

By single crystal X-ray analysis, the atomic structure of the crystals of bis-phenanthrolinium hexachlorotellurate(IV) dihydrate (ɋ 12 ɇ 9 N 2 ) 2 TeBr 6 2H 2 O (a = 7.4846(5) Å, b = 13.792(1) Å, c = 14.532(1) Å, E = 99.857(2)°, space group Ɋ2 1 /c, Z = 2, d x = 2.259 g/cm 3 ) is determined. The crystal structure is formed from separate anions [TeBr 6 ] 2-, cations of phenanthrolinium (ɋ 12 ɇ 9 N 2 ) + , and water molecules. The electronic and geometrical aspects determining the spectral-luminescent and thermochromic properties of the complex are discussed.Due to the intense luminescence of mercury-like ions with the s 2 configuration of the outer electron shell (for example, Sb 3+ , Te 4+ , etc.) it is possible to use them as effective luminophores for luminescence lamps, cathodo-and X-ray phosphors [1][2][3]. While the luminescence of the solutions of simple halide salts of s 2 ions and crystalline phosphors doped by them has been examined in considerable detail, information on the luminescent properties of complex compounds of this class is limited [4][5][6].This work is the continuation of the study of the relationship between the structure and spectral luminescent characteristics of tellurium(IV) complexes with nitrogen-containing outer-sphere organic cations [7,8]. The work is devoted to the synthesis of (ɋ 12 ɇ 9 N 2 ) 2 TeBr 6 2H 2 O (I) complex, its crystal structure examination, and the relationship between the optical and luminescent properties and the features of its electronic and geometrical structure. EXPERIMENTALCompound I was synthesized in the interaction of freshly prepared solutions of TeO 2 and 1,10-phenanthrolinium (ɋ 12 ɇ 8 N 2 ) in the concentrated HBr medium on heating. The produced solutions were mixed; the reaction mixture was evaporated in a water bath and then cooled at room temperature. The residue was filtered off and dried in a desiccator above NaOH until reaching a constant weight. The crystals of compound I are red-brown, insoluble in ɇ 2 Ɉ and non-polar organic solvents and soluble in polar organic media. The ɋ, ɇ, N, and Br analysis of the produced compounds was performed using the well-known techniques: ɋ, ɇ, N by a semi-micro method; the bromide concentration was determined titrimetrically by the Folgard method [9].Luminescence spectra at 77 K were recorded on a SDL-1 spectrometer. As an excitation source, a DRS-250 mercury lamp was used. Reflection spectra were recorded at 100 K and 300 K on a Hitachi U 3010 spectrometer.

Luminescent Properties of Complexes of Tellurium(IV) Halides with Pyridine (C5H5NH)2TeHal6 (Hal = Cl, Br)

“…The present work continues our investigations of the relation between the structure and the spectralluminescent properties of tellurium(IV) halide complexes [7,22,23,[25][26][27][28][29][30]. The correlation between the geometric structure and the spectral-luminescent properties is studied on the example of hexahalotellurate(IV) complexes with pyridine of the composition (C 5 H 5 NH) 2 TeHal 6 (Hal = Cl, Br)…”

Люминесцентные свойства комплексов галогенидов теллура (IV) с пиридином (C-=SUB=-5-=/SUB=-H-=SUB=-5-=/SUB=-NH)-=SUB=-2-=/SUB=-TeHaI-=SUB=-6-=/SUB=- (где HaI=Cl, Br)

“…Настоящая работа является продолжением наших исследований взаимосвязи строения и спектральнолюминесцентных свойств галогенидных комплексов теллура (IV) [7,22,23,[25][26][27][28][29][30]. На примере гексагалотеллуратов (IV) пиридиния состава (C 5 H 5 NH) 2 TeHa l6 (где Hal=Cl, Br) изучена взаимосвязь геометрического строения и спектрально-люминесцентных свойств.…”

Люминесцентные и термохромные свойства комплексов галогенидов теллура(IV) с рубидием Rb-=SUB=-2-=/SUB=-TeHal-=SUB=-6-=/SUB=- (Hal = Cl, Br, I)

“…В работах [2,22] показано, что люминесценция комплексных соединений теллура(IV) определяется не чисто электронными p → s-переходами иона Те(IV), важный вклад в люминесцентные процессы вносят атомные p-орбитали галогенид-ионов. В работах [3,[23][24][25][26][27][28][29][30] обнаружены обратимые термохромные свойства комплексных соединений s 2 -ионов (Sе 4+ , Те 4+ , Sb 3+ ).…”

“…Анализ литературных данных показал, что в отличие от галогенидных комплексных соединений сурьмы(III) и висмута(III), для которых обнаружено большое многообразие типов анионных подрешеток [31], для большинства галогенидных соединений теллура(IV) характерно, как правило, островное октаэдрическое строение анионной подрешетки с минимальными искажениями координационного полиэдра иона теллура(IV) [3,[24][25][26][27][28][29][30][32][33][34].…”

“…Настоящая работа является продолжением наших исследований взаимосвязи строения, спектральнолюминесцентных и термохромных свойств галогенидных комплексов теллура(IV) [3,22,[24][25][26]28,29,35,36]. На примере комплексных гексагалотеллуратов(IV) рубидия состава Rb 2 TeHal 6 (Hal = Cl, Br, I) изучена взаимосвязь геометрического строения, спектрально-люминесцентных и термохромных свойств.…”