Synthesis and spectroscopic investigations of a crystalline humidity sensor:: Bis(triphenylphosphine) iminium 2,2′-bipyridyltetracyanoruthenate

被引:62
作者
Evju, JK [1 ]
Mann, KR [1 ]
机构
[1] Univ Minnesota, Dept Chem, Minneapolis, MN 55455 USA
关键词
D O I
10.1021/cm980323i
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
We have prepared a new salt of the solvatochromic [Ru(bpy)(CN)(4)](2-) anion bis(triphenylphosphine)iminium 2,2'-bipyridyltetracyanoruthenate, ((PPN)(2)[Ru(bpy)(CN)(4)]), that reversibly sorbs water and changes color from purple to yellow when it is exposed to humid air. Solid samples of anhydrous (PPN)(2)[Ru(bpy)(CN)(4)] reversibly hydrate in humid air, first to (PPN)(2)[Ru(bpy)(CN)(4)] . H2O and then to (PPN)(2)[Ru(bpy)(CN)(4)]. 15H(2)O. A single-crystal X-ray study of(PPN)(2)[Ru(bpy)(CN)(4)]. 2CH(3)CN . 2(CH3CH2)(2)O . 2H(2)O shows that this novel humidity sensor has large channels in the structure that allows sorbed water molecules to reversibly interact with the cyanide ligands of the chromophore. The hydration changes that result from exposure of the solid in the 0 to 66% relative humidity range cause the MLCT visible absorption bands to shift dramatically to higher energy. These hydration changes also result in large shifts in the v(CN) region of the infrared spectrum; these changes indicate significant H-bonding interactions between sorbed water molecules and the dianionic chromophore occur in the crystal lattice. The hydration changes in the 66 to 100% relative humidity range cause large intensity changes in a visible photoluminescence band. This emission intensity increase is accompanied by small wavelength shifts in absorption and emission and in the v(CN) region of the infrared spectrum. These changes are consistent with further oligomerization of the water molecules that initially formed hydrogen-bonding interactions to the cyanide ligands.
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页码:1425 / 1433
页数:9
相关论文
共 57 条
[1]  
ATWOOD JL, 1984, INCLUSION COMPOUNDS, V2, P123
[2]   FAST HUMIDITY RESPONSE OF A METAL HALIDE-DOPED NOVEL POLYMER [J].
BEARZOTTI, A ;
DAMICO, A ;
FURLANI, A ;
IUCCI, G ;
RUSSO, MV .
SENSORS AND ACTUATORS B-CHEMICAL, 1992, 7 (1-3) :451-454
[3]   ARENE RUTHENIUM(II) COMPLEXES FORMED BY DEHYDROGENATION OF CYCLOHEXADIENES WITH RUTHENIUM(III) TRICHLORIDE [J].
BENNETT, MA ;
SMITH, AK .
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1974, (02) :233-241
[4]   A SIMPLE POLY(PYRIDINE)RUTHENIUM(II) PHOTOSENSITIZER - (2,2'-BIPYRIDINE)TETRACYANORUTHENATE(II) [J].
BIGNOZZI, CA ;
CHIORBOLI, C ;
INDELLI, MT ;
SCANDOLA, MAR ;
VARANI, G ;
SCANDOLA, F .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1986, 108 (24) :7872-7873
[5]  
BINSTEAD RA, 1995, SPECFIT V2 09
[6]  
BLASSE G, 1994, LUMINESCENT MAT, pA225
[7]   DEVELOPMENT OF AN OPTICAL RELATIVE-HUMIDITY SENSOR - COBALT CHLORIDE OPTICAL ABSORBENCY SENSOR STUDY [J].
BOLTINGHOUSE, F ;
ABEL, K .
ANALYTICAL CHEMISTRY, 1989, 61 (17) :1863-1866
[8]  
BUDAVARI S, 1989, MERCK INDEX, P9954
[9]   Structural investigations of vapochromic behavior.: X-ray single-crystal and powder diffraction studies of [Pt(CN-iso-C3H7)4][M(CN)4] for M = Pt or Pd [J].
Buss, CE ;
Anderson, CE ;
Pomije, MK ;
Lutz, CM ;
Britton, D ;
Mann, KR .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1998, 120 (31) :7783-7790
[10]   APPLICATION OF THE ENERGY-GAP LAW TO NONRADIATIVE, EXCITED-STATE DECAY [J].
CASPAR, JV ;
MEYER, TJ .
JOURNAL OF PHYSICAL CHEMISTRY, 1983, 87 (06) :952-957