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Citation: . STUDY ON STABILITY OF STRUCTURE AND PROPERTIES OF TIOPC/SAN PHOTOCONDUCTIVE COMPOSITES[J]. Chinese Journal of Polymer Science, ;2003, 21(5): 515-520. shu

STUDY ON STABILITY OF STRUCTURE AND PROPERTIES OF TIOPC/SAN PHOTOCONDUCTIVE COMPOSITES

  • Received Date: 3 March 2003

  • The influence of the condensed structure of poly(styrene-co-acrylonitrile) (SAN) and traces of tetrahydrofuran(THF) that remained in titanyl phthalocyanine (TiOPc)/SAN films after fabrication on the photoconductive stability ofTiOPc/SAN composites is studied. The results reveal that the existence of traces of THF results in the increase of thephotoconductivity and the charging voltage. The main facors responsible for the unstable photoconductivity of thephotoconductors are believed to be the relaxation of SAN and the slow volatilization of THF.
  • In the latest decade, metallochalcogenides have attracted great attention owing to their peculiar attributes, such as luminescence, semiconduction, ion-exchange, magnetism, and uranium removal[1-10]. For instance, ZnIn2S4[11] and oxidized SnS2[12] sheets exhibit high-efficiency carbon dioxide (CO2) reduction performances under visible-light illumination. Among them, unlike dense and bulky phase materials as three-dimensional CdS or layered MoS2, open-framework chalcogenidometalates, mainly constructed from supertetra-hedral clusters (denoted as Tn, Cn, Pn, Tp, q, OTn and so on by Feng et al.)[13], have unique cooperative effects combining absorption-based capture, optoelectronic nature, and quantum-dot structure, which could lead to new applications and currently are being intensively investigated[14, 15]. Up to now, a huge number of supertetrahedral metallochalcogenides and their open-frameworks have been obtained. However, to our knowledge, quite few organometal chalcogenides were reported[16, 17]. Herein, we have attained linear {Butyl-Sn4S8} tetramer, which could serve as linker to coordinate with two metal complexes (Mn-TEPA or Ni-TEPA, where TEPA = tetraethylenepentamine), constructing a ribbon-like hexameric structure ((butyl-Sn)4S8M2(TEPA)2, denoted as 1 and 2, when M = Mn and Ni, respectively). Magnetic measurements were conducted to show that both 1 and 2 show ferromagnetic-like behavior, with the Weiss (θ) values and the intradimer coupling constants (J) up to 8.5 K and 6.8 cm-1 for 1 and 21.1 K and 17.2 cm-1 for 2, respectively.

    All reagents were obtained from commercial sources and used without further purification. Elemental analyses (EA) for C, H, and N were carried out on a German Elementary Vario EL III instrument. Infrared (IR) spectra were collected on a PerkinElmer spectrometer with KBr pellets (range, 500~4000 cm-1). Ultraviolet-visible (UV-Vis) diffuse reflection spectra (DRS) were recorded on a PerkinElmer Lamda-950 UV spectrophotometer with BaSO4 substrates (range, 200~800 nm). Energy dispersive X-ray (EDX) spectra were acquired by a JSM-6700F scanning electron microscope. Thermogravimetric analyses (TGA) were measured on a NETZSCH STA 449F5 thermal analyzer under N2 atmosphere (range, 30~800 ℃; heating rate, 10 ℃∙min-1). Powder X-ray diffraction (PXRD) data were performed on a Rigaku miniFlex II diffractometer with Cu- (λ = 1.54056 Å) in the 2θ range of 3~50° (scan speed, 1 °∙min-1). Variable-temperature and field-dependent magnetization data were conducted on a Quantum Design MPMS-XL magnetometer (temperature range, 2~300 K; magnetic field range, 0~50 kOe; experimental susceptibilities were corrected for the diamagnetism of the constituent atoms by use of Pascal's tables).

    1-(butyl-Sn)4S8Mn2 (TEPA)2 was synthesized from solvothermal method by adding methanol (MeOH, 2 mL), n-butylSnCl3 (50 μL) and tetraethylenepentamine (TEPA, 2.5 mL) into a mixture of Mn(OAc)2·4H2O (221.2 mg, 0.91 mmol) and sulfur (S, 32 mg, 1 mmol) in a 20 mL vial, and heated to 80 ℃ for 7 days. Light-yellow block-shaped crystals were collected after cooling to room in ca. 43% yield based on S. EA data for C32H82N10S8Sn4Mn2 (1): Calcd. (%): C, 26.57; H, 4.46; N, 9.69. Found (%): C, 26.55; H, 5.53; N, 9.66. IR (KBr, cm-1): 3290(m), 3224(m), 3162(m), 2952(m), 2908(m), 2854(m), 2349(w), 2160(w), 2096(w), 1963(w), 1660(m), 1581(m), 1458(m), 1365(m), 1286(m), 1242(m), 1207(m), 1174(m), 1116(m), 1085(m), 995(s), 939(s), 871(m), 821(m), 682(m), 574(m), 493(s).

    2-(butyl-Sn)4S8Ni2(TEPA)2 was synthesized from solvother-mal method by adding distilled water (2 mL), n-butylSnCl3 (50 μL) and TEPA (2.5 mL) into a mixture of Ni(OAc)2·4H2O (223.1 mg, 0.91 mmol) and sulfur (S, 33.1 mg, 1 mmol) in a 20 mL vial and heated to 80 ℃ for 7 days. Light-purple block-shaped crystals were collected after cooling to room in ca. 57% yield based on S. EA data for C32H82N10S8Sn4Ni2 (2): Calcd. (%): C, 25.88; H, 4.31; N, 9.74. Found (%): C, 26.37; H, 5.73; N, 9.60. IR (KBr, cm-1): 3332(m), 3245(m), 3157(m), 3120(m), 2948(m), 2898(m), 2852(m), 1714(w), 1629(m), 1579(m), 1456(m), 1373(m), 1340(m), 1286(m), 1243(m), 1143(m), 1083(m), 1054(m), 1008(m), 941(s), 881(m), 767(m), 678(m), 563(m), 486(m), 422(m).

    Single crystals of suitable size were selected and mounted on a glass fiber. Single-crystal X-ray diffraction (SCXRD) data were collected on a Rigaku Saturn724+ diffractometer equipped with graphite-monochromatized Mo- radiation (λ = 0.71073 Å) at 298 K. Absorption corrections by the multi-scan method were applied. The structures were solved by direct methods with SHELXS-97 program and refined on F2 by full-matrix least-squares methods using SHELXL-2014 program package embedded in OLEX2. All non-hydrogen atoms were located with successive difference Fourier technique and refined anisotropically. Hydrogen atoms were added in the idealized positions and refined with isotropic parameters. The final R = 0.0629, wR = 0.1285 for 12855 observed reflections (I > 2σ(I), w = 1/[σ2(Fo2) + (0.0333P)2 + 0.0412P], where P = (Fo2 + 2Fc2)/3), S = 1.001, (Δ/σ)max = 0.001, (Δρ)max = 1.63 and (Δρ)min = –0.88 e·Å-3 for 1-(butyl-Sn)4S8Mn2. The final R = 0.0464, wR = 0.1185 for 9267 observed reflections (I > 2σ(I), w = 1/[σ2(Fo2) + (0.0333P)2 + 0.0412P], where P = (Fo2 + 2Fc2)/3), S = 1.017, (Δ/σ)max = 0.001, (Δρ)max = 1.19 and (Δρ)min = –0.87 e·Å-3 for 2-(butyl-Sn)4S8Ni2. Selected bond lengths and bond angles from X-ray structure analyses are listed in Table S2~S5 (SI).

    SCXRD analyses revealed that both compounds 1 and 2 crystallize in the triclinic P¯1 space group, and possess the same building units of hexamer {(Butyl-Sn)4S8(M-TEPA)2} (M = Mn for 1, and Ni for 2). In each asymmetric unit, there are four bridged S2- linkers, one [Mn-TEPA]2+ and two [butyl-Sn]3+ moieties. Ligands of TEPA are not deprotonated during the self-assembly process. Sn1 and Sn2 adopt different coordination modes: Sn1 links to three μ2-S2- atoms and one butyl group, while Sn2 bonds four μ2-S2- atoms and one butyl group. As shown in Figs. 1 and 2, the paramagnetic-ions Mn2+ and Ni2+ are coordinated by one μ2-S2- atom and five N atoms from a same TEPA amine in a distorted octahedron of coordination geometry. Two [M-TEPA]2+ complexes are connected via long chain of [Sn4S8] to form a hexamer {(Butyl-Sn)4S8(M-TEPA)2} (M = Mn for 1, and Ni for 2), with the distances between terminal transition metals to be 13.485 and 14.078 Å for 1 and 2, respectively. However, complexes 1 and 2 possess different packing fashions through hydrogen bonding interactions (N–H⋅⋅⋅S) (Fig. 1b and 2b, Figs. S1 and S2 in SI), which are in the ranges of 2.438~2.479 Å for 1 and 2.410~2.545 Å for 2, respectively.

    Figure 1

    Figure 1.  (a) Crystal structure and polyhedral drawing of compound 1-(butyl-Sn)4S8Mn2; (b) Hydrogen-bonding interaction of 1; (c) Packing mode of 1 along with [100] direction. Hydrogen atoms were omitted for clarity in a and c

    Figure 2

    Figure 2.  (a) Crystal structure and polyhedral drawing of compound 2-(butyl-Sn)4S8Ni2; (b) Hydrogen-bonding interaction of 2; (c) Packing mode of 2 along with [010] direction. Hydrogen atoms were omitted for clarity in a and c

    Confirmed by PXRD (Fig. 3a and 4a), we can conclude that phase purities of 1-(butyl-Sn)4S8Mn2 and 2-(butyl-Sn)4S8Ni2 are quite good since the experimental patterns match well with the simulated ones. As shown in Fig. 3b and 4b, structures 1 and 2 could be stable up to 200 ℃ under N2 atmosphere. Calculated by the extrapolation of the linear part of [Ahv]2 plot of the transformed Kubelka-Munk spectra in Fig. 3c and 4c, their band gaps are 3.097 and 3.325 eV for 1 and 2, respectively. From the FT-IR spectra collected in Fig. 3d and 4d, all the significant peaks could be attributable to the stretching vibration of TEPA, butyl, and the related solvents. EDX spectroscopy was also used to testify the chemical composition of 1 and 2, as shown in Fig. 5.

    Figure 3

    Figure 3.  Powder XRD patterns (a), TGA plot (b), FT-IR spectrum (c), and transformed Kubelka-Munk UV-Vis spectrum (d) of compound 1-(butyl-Sn)4S8Mn2

    Figure 4

    Figure 4.  Powder XRD patterns (a); TGA plot (b); FT-IR spectrum (c); and transformed Kubelka-Munk UV-Vis spectrum (d) of compound 2-(butyl-Sn)4S8Ni2

    Figure 5

    Figure 5.  EDX spectra of compounds (a) 1-(butyl-Sn)4S8Ni2; and (b) 2-(butyl-Sn)4S8Ni2

    The temperature dependences of the magnetic susceptibility of 1-(butyl-Sn)4S8Mn2 and 2-(butyl-Sn)4S8Ni2 in the 2~300 K temperature range are plotted in Fig. 6. For 1, the experiment χMT value at 300 K is 8.29 cm3∙K∙mol-1, close to the spin-only value (8.75 cm3∙K∙mol-1, S = 5/2) expected for two isolated Mn2+ ions. As the temperature is lowered, χMT value first increases smoothly to 8.74 cm3∙K∙mol-1 at 48 K, indicating a dominant ferromagnetic interaction of the Mn2+ ions, then decreases down to 6.54 cm3∙K∙mol-1 at 2 K. The reciprocal susceptibility χM-1 vs. temperature curve above 50 K obeys the Curie-Weiss law, with the Curie value (C) of 8.15 cm3∙K∙mol-1 and Weiss constant (θ) being 8.5 K, indicating an overall ferromagnetic behavior in 1. Sample 2 exhibits the same magnetic phenomenon as 1. The χMT value at 300 K is 1.93 cm3∙K∙mol-1, which is also close to the spin-only value (2.00 cm3∙K∙mol-1, S = 1) expected for two isolated Ni2+ ions. As the temperature is lowered, the χMT value first rises to 2.22 cm3∙K∙mol-1 at 36 K, and then drops upon further cooling. In addition, its C and θ values were calculated to be 1.87 cm3∙K∙mol-1 and 21.1 K, respectively. Based on the structural feature, the magnetic susceptibility data of 1 and 2 could be analyzed by using a dinuclear model (isotropic Hamiltonian equation of Ĥ = –2JSASB, where J is for the intradimer coupling constant), in which the contribution of the intermolecular interaction (zJ') is also taken into account. The least-squares fitting of the magnetic susceptibility data gives the following parameters: J = 6.8(7) cm–1, zJ' = –0.3(5) cm–1, g = 2.02(3) and R = 1.5 × 10–4 for 1; J = 17.2(8) cm–1, zJ' = –0.8(4) cm–1, g = 2.07(4) and R = 2.1 × 10–4 for 2, respectively. These values further confirm the ferromagnetic interaction character between the Mn2+ or Ni2+ ions via the tetrameric {butyl-Sn4S8} bridges.

    Figure 6

    Figure 6.  Magnetic properties of compounds 1-{Mn2} (a) and 2-{Ni2} (b): Temperature dependence of the χMT product (red scatter, where the black line represents the isotropic Hamiltonian fitting), and the χM-1 vs. T (blue scatter, where the black line represents the Curie-Weiss fitting) with inset of the magnetization curve

    In summary, we report herein the synthesis, structure and magnetic properties of two organotin-sulfide-spaced dimers {Mn2} (1) and {Ni2} (2) terminated by TEPA. Both 1 and 2 feature similar structures of tetrameric {butyl-Sn4S8}, which further connects two Mn-TEPA (1) or Ni-TEPA complexes (2), respectively. Notably, complexes 1 and 2 exhibit an overall ferromagnetic-like behavior.


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