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【期刊论文】Synthesis, structure and electrical conductivity of (PyMe)[Ni(dmit)2]2
方奇, Wen Xu a, Qi Fang a, *, Hong-Yu Chen a, Gang Xue a, Guo-Qun Liu a, Wen-Tao Yu a, Jin-Biao Zhang b, Cui-Ying Xu b, De-Qing Zhang b, Dao-Ben Zhu b
Inorganic Chemistry Communications 7(2004)531-533,-0001,():
-1年11月30日
A new molecular conductor (PyMe)[Ni(dmit)2]2 (PyMe=N-methylpyridinium, dmit= 2-thioxo-1,3-dithiole-4,5-dithiolato) has been synthesized and its structure been determined. The temperature-dependent conductivities in the range of 290-20K reveal a semi-conducting behavior of the crystal with a small activation energy of 0.067 eV and a quite high room temperature conductivity of 2 Scm 1.
Nickel complex, Synthesis, X-ray crystal structure, Semiconductors
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方奇, Du-Xia Cao, [a] Qi Fang, *[a] Dong Wang, [a] Zhi-Qiang Liu, [a] Gang Xue, [a] Gui-Bao Xu, [a] and Wen-Tao Yu [a]
Eur. J. Org. Chem. 2003, 3628-3636,-0001,():
-1年11月30日
We have synthesized a series of new D−π−A compounds that feature various electron donors and a fixed benzothiazolyl unit as an electron acceptor. The crystal structure of compound 3 [trans,trans-2-{4-[(4-N-carbazolyl)styryl]styryl}-1,3-benzothiazole, CSSB] was determined. All these compounds show high fluorescence quantum yields and 3 in toluene gives the most intense blue emission around 450 nm with a quantum yield of Φ = 0.69. When excited at 800 nm by a Ti: sapphire femtosecond laser, these compounds exhibit strong two-photon-excited fluorescence (TPEF) in the blue-to-orange region. The measured TPEF cross-section of compound 2 [trans,trans-2-{4-[4-(N,N-diphenylamino)styryl]- styryl}-1,3-benzothiazole, DPSSB], for example, is about 6.1 times that of Coumarin 307. hotophysical data indicate that these compounds are polar in the ground state and have an enhanced polarity in the excited state, and that the electron donating ability of a dialkylamino group is much stronger than that of a diarylamino group.
Fluorescence, Sulfur heterocycles, Wittig reactions
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方奇, Zhi-qiang Liu, [a] Qi Fang, *[a] Dong Wang, [a] Du-xia Cao, [a] Gang Xue, [a] Wen-tao Yu, [a] and Hong Lei [b]
Chem. Eur. J. 2003, 9, 5074-5084,-0001,():
-1年11月30日
The synthesis, structure, and fluorescence properties of a series of new donor -π- acceptor (D-π-A) type compounds, with a trivalent boron, protected by two mesityl groups, as acceptor, and with various typical donors and different-conjugated bridges, are reported. All these stable organoboron compounds show intense singlephoton excited fluorescence (SPEF) and two-photon excited fluorescence (TPEF) in a wide spectral range from blue to green, with the spectral peak position of the SPEF being basically the same as that of the TPEF. The remarkably strong C B(mesityl)2 bonding, and the well-conjugated -system, shown in X-ray crystal structures of two compounds, indicate some charge transfer features of the ground state. Meanwhile, spectral data indicate that the charge transfer from donor to acceptor is greatly enhanced in the excited states. Based on typical structural data and comprehensive spectral data, the following structure-property relationships can be drawn: 1) the moderate arylamino donor can more effectively enhance the SPEF and TPEF intensities than can the strong alkylamino donor; 2) stilbene is a better-bridge than styrylthiophene for its capability of enhancing and blueshifting the SPEF and TPEF of the corresponding D-π-A compounds; and 3) when compared to its boron-free precursors and other analogues, -B(mesityl) 2 invariably and consistently acts as an effective SPEF and TPEF fluorophore in all this series of organoboron compounds, which may result from its strong-electron-withdrawing and charge transfer-inducing nature in the ground-state and, more dominantly, in the excited-state. Combining all the above positive structure factors, trans-4-N,N-diphenylamino-4-dimesitylborylstilbene (compound 3) stands out as the optimized green SPEF and TPEF emitter. This compound exhibits an SPEF quantum yield of 0.91 at 522 nm in THF, a TPEF cross-section that is an order of magnitude larger than that of its boron-free precursor upon excitation by 800nm femto-second laser pulses, and a two-photon absorption section of 3.0 10 48 cm4 s. In the blue light region, trans-4 -N-carbazolyl-4-dimesitylborylstilbene (compound 4) shows significant SPEF and TPEF properties, with 0.79 at 464 nm in THF and a large value, which is five times that of fluorescein upon excitation by 740 nm femto-second laser pulses.
boron, donor, acceptor systems, electron-deficient compounds, fluorescence
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方奇, Fang Qi, *, a, b Thomas C. W. Mak, b Zhou Zhong-Yuan, b Yang Qing-Chuan, b Liu Zhi, a Yu Wen-Tao, a Zhu Dao-Ben c and Jiang Min-Hua a
J. Chem. Soc., Dalton Trans., 2002, 1377-1385,-0001,():
-1年11月30日
Electrically conductive platelet crystals of Z[Pd(dmit)2]2 [Z = (Me3NEt), (MeNEt3), (NEt4)], as well as their precursors Z2 [Pd (dmit) 2], have been synthesized by a non-electrochemical method and their structures have been determined. The single-crystal conductivities at a direction on the cleavage surface at room temperature were measured to be 58 Ω 1 cm 1 for (Me3NEt)[Pd(dmit)2]2, 5.0 Ω 1 cm 1 for (MeNEt3)[Pd(dmit)2]2 and 2.2 Ω 1 cm 1 for (NEt4)[Pd(dmit)2]2, respectively. This sequence of conductivity is agreement with the sequence of structural twodimensionality of these three complexes. The resistivity–temperature curves reveal the semiconducting behavior of the above complexes, which show very narrow band gaps. The structure analysis results reveals that when the size of cation Z in Z[Pd(dmit)2]2 is finely tuned [(Me4N)+→(Me3NEt)+→(Me2NEt2)+→(MeNEt3)+→(NEt4)], the corresponding complexes belong to the same structural motif and each individual possesses some special structural characteristics. Subtle structural difference in this group of complexes can severely influence their measured conductivities and significantly influence their calculated band structures.
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方奇, Y.Z. Cui a, b, Q. Fang a, *, H. Lei c, G. Xue a, W.T. Yu a
Chemical Physics Letters 377(2003)507-511,-0001,():
-1年11月30日
Three compounds with three p-substituted styryls attaching to the central s-triazine have been synthesized and two crystals determined to be in non-centrosymmetric Cmc21 and Pmn21 space groups, respectively. All of them in solid state are second harmonic generation (SHG) active and two of them show powder SHG intensities one order of magnitude that of urea.
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