Structures, Photoluminescence, and Reversble ：结构光致发光和可逆性

1、1structures, photoluminescence, and reversible vapoluminescence properties of neutral platinum(ii)complexes containing extended -conjugated cyclometalated ligandssteven c. f. kui, stephen sin-yin chui, chi-ming che,* and nianyong zhupresenter : 戴如妮j. am. chem. soc. 2006, 128, 8297-80392holliday, b.

2、j. et. al. angew. chem. int. ed. 2001, 40, 2022-2043.supramolecular coordination chemistryhydrogen bondingp p-p p interactionmetal to ligand bindingvan der waals forces3stang, p. j.; olenyuk, b. acc. chem. res.; 1997, 30, 502-518supramolecular assembly of polyhedrac-h p pp p p p4hcnn = 4-(4-tolyl)-6

3、-phenyl-2,2-bipyridineyang, q. -z. et. al. inorg. chem. 2004, 43, 5195.ch3cn (1.2x10-5m)mg(cnn)pt(ii) complex containing a monoaza-15-crown-5h3cnnptnoooophotoinduced electron transfer (pet)5organoplatinum crystals forgas-triggered switcheskoten, g. v. et. al. nature. 2000, 406, 970-974.ptme2hnnhme2c

4、l+ so2- so2ptme2hnnhme2clso26(i) the facile reversible change of the molecular structure of the luminophore(ii) alterations in the molecular packing when the analyte molecule enters and exits the crystal structure of the luminescent sensory material.a) eisenberg, r. et. al. j. am. chem. soc. 2004, 1

5、26, 16841-16849.b) william, b. c. et. al. j. am. chem. soc. 2004, 126, 1594-1595.volatile organic compounds ( vocs )vapoluminescencea)b)7crystal structure of (cnc)2pt2(-dppm)(cnc)2pt2(-dppm)(cnc)2pt2(-dppm)chcl3pphphptnccpphphptnccb(cnc)2pt2(-dppm)anti-chcl3che, c.-m. et. al. organometallics. 2001,

6、20, 2477-2486.p(1)-pt(1)-n(1) = 170.6(2)p(2)-pt(2)-n(2) = 172.4(2)p(1)-pt(1)-n(1) = 171.2(2)p(2)-pt(2)-n(2) = 174.6(3)8(r-cnc)2pt2(-dppm)(r-cnc)pt(dmso)(ph-cnc)pt(pph3)rourkes methodrourke, j. p. et. al. organometallics. 2000, 19, 1355-1364.(r-cnc)pt(l)nccptlrncck2ptcl4acohrefluxed for48 hnccptclclp

7、tncchot dmsoh2orrrnccptsorr = h, 2a; ph, 2b; 4-brc6h4, 2c; 3,5-f2c6h3, 2d2n2nptsorr = h, 4a; ph, 4b; 4-brc6h4, 4c; 3,5-f2c6h3, 4d2+dppmch2cl212 h4pphphptnccpphphptrnccrn2nccptsoph2b+pph3ch2cl212 hnccptph3pphphph9simulated 31p1hnmr spectra of 4b insyn- and anti-syn-anti-simulated based on aaxx system

8、, 31p nmr (162 mhz,cd2cl2)( d, 1jp-195pt = 4236.36 hz )( d, 2jp-p = 34.91 hz )(d, 2jp-195pt = 84.41 hz)(d, 3jp-195pt = 29.0 hz )( d, 1jp-195pt = 4236.36 hz )( d, 2jp-p = 34.91 hz )(d, 2jp-195pt = 84.41 hz)(d, 3jp-195pt = 29.0 hz )( d, 1jp-195pt = 4236.36 hz )( d, 2jp-p = 34.91 hz )(d, 2jp-195pt = 84

9、.41 hz)(d, 3jp-195pt = 29.0 hz )1031p1h nmr spectrum of 4b in cd2cl2 experimentsyn-isotopenatural abundance/%spin of nucleus190pt0.01192pt0.79194pt32.9195pt33.81/2196pt25.3198pt7.24bpphphptnccpphphptphnccph( d, 1jp-195pt = 4251.0 hz )11the structures of 2b, 3, 4bnccptsoph2bnccptph3pphphph4bpphphptnc

10、cpphphptphnccph122b excimeric (a-a*) 3* excited states 4b excimeric 3*excited states3 intraligant 3*excited statesuv-vis absorption and solid-state emission spectra of 2b, 3, and 4b at r. t.charge transferd-d transitionmetal-metal (d-d) transitionmetal-ligand charge transfer ligand-metal charge tran

11、sferligand-ligand transitions s*metal dnligand p s sligand p*nmetal d13emission spectra of 2b & 4bvibronic coupling interaction between electronic and vibrational modes, increase intensity4bpphphptnccpphphptphnccph2b in the solid state at 77 kin 2-methf at 77 ka)4b in the solid state at 77 k in

12、2-methf at 77 kb)nccptsoph2b14emission spectra of 3emission spectra of 3 in the solid state at room temperature, 77 k, and as a glassy solutionin 2-methf at 77 knccptph3pphphph15the emission spectra of 4b at various temperaturenon - emissionemission spectra of 4b in 2-methf solution at 103-263 k523

13、nm566 nm(i) the molecular motion of the flexible pt-p-ch2-p-pt unit (ii) the presence of a low-lying non-emissive d-d excited state4bpphphptnccpphphptphnccph16solid 4a under ambient light and under uv light irradiationanbient lightuv lightsolid 4a under ambient light and under uv light irradiation (

14、350 nm). (a) orange crystals of 4a upon exposure to air. (b) a reversible vapoluminescence for the desolvated form of 4a within 1 min of being exposed to chcl3 vapor.b)a)17vapoluminescent behavior of 4aivoc is the emission intensity of desolvated 4a upon exposure to voc under saturation conditions i

15、desolvate is the emissionintensity of desovated 4a4apphphptnccpphphpthncch18the crystal structure for 2aperspective view of 2a with omission of hydrogen atoms (left) and the head-to-tail pairs molecular orientation (right).nccptsoh2a19the crystal structures for 2b & 2cperspective view of 2bchcl3

16、 & 2cch2cl2 with the omission of hydrogen atoms. 2b.chcl32c.ch2cl2nccptso2bnccptso2cbr20perspective view of syn - and anti - 4a.6chcl3.c5h12syn -pphphptnccpphphpthncchpphphptnccpph phptnccanti -c-hc-h(solvent)c-hx21solvent channels6.5 x 4.3 porous molecular structure of 4a6chcl3c5h12syn-anti-22t

17、he structures of 4c & 4dsolvent channels7.4 x 2.8 solvent channels4.6 x 2.0 syn - 4c3ch2cl2anti - 4d2chcl34cpphphptnccpphphptnccbrbrpphphptnccpphphptncc4dffff23(hkl)q2qcompared with pxrd of structures of solvated and desolvated 4a/xray/tutorial/ewald.htmewald sphereloss o

18、f solvent2q 2q = 5.877ovolume = 6188 3 2q 2q = 5.297ovolume = 7374 3 24layer of syn-moleculeslayer of anti-moleculeslayer of syn-moleculeslayer of anti-moleculeslayer of syn-moleculespacking diagram of desolvated 4amolecular packing within desolvated 4a viewed from the c-axis4apphphptnccpphphpthncch

19、25the vapoluminescent propertiesfor solvated & desolvated 4ag = h t .sloss of solvent26conclusions mononuclear and dinuclear cyclometalated (r-cnc)pt-l complexes were prepared and structurally characterized. accessible solvent channels and the presence of weak and reversible non-covalent c-h , ,

20、c-hx, and xx interactions account for the vapoluminescent behavior of 4a. the sensitivity of the emission properties of squar planar pt(ii) complexes is the basic operating principle behind their application as molecular voc sensory materials.(r-cnn) pt(r)1mlct3mlcthvintersystem crossingkrknrs0s1t1e

21、xcimers excited-state dimersexcimeric (a-a*) 3* /wiki/excimera+ e-a+2e-a+ 2e-a-a*+e-+ avibronic coupling1.when there is an atom common to the two vibrations.2.bending vibrations requires a common bond between the vibrating groups.3.the stretching bond forms one side of the angle that varies in the bending vibration.4.the coupled groups have individual energies that are approximately equal.is a short-lived