杨洪芳,孔令乾
YANG Hong-fang,KONG Ling-qian

• 1:德州学院纺织服装学院

摘要(Abstract)：

目前市面上电磁功能纺织品的磁性大都来自于染色、涂覆、整理等过程中磁性微粒的额外添加,但上述方法赋予纺织品一定程度磁性的同时持久性较差。研究了纤维素基磁性材料结构基元纤维二糖分子的原始态和甲基化修饰态,意图得到本身固有磁性的纤维素纤维。具体地说,是将纤维二糖分子2号位碳原子上仲羟基的氢原子替换为甲基基团,得到甲基化修饰的纤维二糖分子。DFT表明,甲基化修饰使纤维二糖分子的能量基态由三重态转变为开壳层破损态单重态;同时,磁性耦合常数由原始态的1.23 cm~(-1)变为甲基化修饰态的-0.65 cm~(-1),正值变为负值也意味着体系从铁磁性到反铁磁性的磁性转变。经过甲基化修饰,该体系可作为构建具有长久磁性的新型磁性纤维材料的结构基元。
Currently, magnetic properties of magnetic functional textiles almost all originate from the addition of stationary magnetic particles during the finishing process of printing and dyeing, such as coating, dyeing and pasting. Although these methods can give textiles certain magnetism, but the same time its durability are poor. This work studied the parent and methylblocks of cellulose-based magnetic materials. The methyl-modified cellobiose is designed by replacing the hydrogen atom of its 2-point secondary hydroxyl group with one methyl group. DFT and CASSCF calculations prove that the methyl modification makes the ground state of cellobiose changing from triplet to open-shell BS singlet state. And the values for the magnetic exchange coupling constant from positive 1.23 cm~(-1) to negative-0.65 cm~(-1) shows an magnetic conversion from ferromagnetic to antiferromagnetic. Through methyl modification, a promising strategy of designing new cellobioseorganic magnetic switches has been provided.

关键词(KeyWords)： 纤维素基磁性材料;甲基化修饰;磁性调控
cellulose-based magnetic material;methyl modification;magnetic control

Abstract:

Keywords:

基金项目(Foundation): 国家自然科学基金项目(51505065);; 山东省自然科学基金项目(ZR2016BL13,ZR2015EQ021);; 山东省高校科技发展计划项目(J16LC55);; 德州学院人才引进项目(2015kjrc22,2015kjrc21)

作者(Author): 杨洪芳,孔令乾
YANG Hong-fang,KONG Ling-qian

DOI: 10.16090/j.cnki.hcxw.20190418.002

参考文献(References)：

• [1]SHIMIZU A,KUBO T,URUICHI M,et al.Alternating covalent bonding interactions in a one-dimensional chain of a phenalenyl-based singlet biradical molecule having kekule?structures[J].Journal of the American Chemical Society,2010,132(41):14421-14428.
• [2]ZHANG Fengying,SONG Xinyu,BU Yuxiang.Redox-modulated magnetic transformations between ferro-and antiferromagnetism in organic systems:rational design of magnetic organic molecular switches[J].Journal of Physical Chemistry C,2015,119(50):27930-27937.
• [3]RAJCA A,MUKHERJEE S,PINK M,et al.Exchange coupling mediated through-bonds and through-space in conformationally constrained polyradical scaffolds:calix[4]arene nitroxide tetraradicals and diradical[J].Journal of The American Chemical Society,2006,128(41):13497-13507.
• [4]YANG Hongfang,ZHAO Jing,SONG Xingyu,et al.Computational design of the magnetism-tunable oligobenzylic carbanion complexes[J].Theoretical Chemistry Accounts,2014,133(4):1460.
• [5]YANG Hongfang,SONG Qisheng,LI Wenchao,et al.Multi-zinc-expanded oligoacenes:an intriguing class of well-defined open-shell singlet diradicals[J].Journal of Physical Chemistry C,2012,116(9):5900-5907.
• [6]NISHIKAWA S,FUJITA S,TSUJI K.Modifier of cellulose fibers and modification method of cellulose fibers:EP,0978585A2[P].1999-08-02.
• [7]BORDEANU N,EYHOLZER C,ZIMMErNMANN T.Surface modified cellulose nanofibrils:European,EP,20080021627[P].2008-12-12.
• [8]SAU A C.Silated polysaccharide process:US,5071978[P].1990-09-28.
• [9]PERROTTA R R,WINTER A H,Coldren WH,et al.2-(3,5-Dinitrophenyl)-1,3-dithiane carbanion:A benzylic anion with a low energy triplet state[J].Journal of the American Chemical Society,2011,133(39):15553-15558.
• [10]LEE C,YANG W,PARR R G.Development of the colle-salvetti conelation energy formula into a functional of the electron density[J].Physical Review B,1988,37(2):785-789.
• [11]BELL F,CASANOVA D,HEAD G M.Theoretical study of substituted pbpb dimers:structural analysis,tetraradical character,and excited states[J].Journal of the American Chemical Society,2010,132(32):11314-11322.
• [12]STAROVEROV V N,DAVIDSON E R.Diradical character of the cope rearrangement transition state[J].Journal of The American Chemical Society,2000,122(1):186-187.
• [13]DUTOI A D,JUNG Y,Head-gordon martin.An orbital-based definition of radical and multiradical character[J].The Journal of Physical Chemistry A,2004,108(46):10270-10279.
• [14]KUBO T,KATADA Y,SHIMIZU A,et al.Synthesis,crystal structure,and physical properties of sterically unprotected hydrocarbon radicals[J].Journal of the American Chemical Society,2011,133(36):14240-14243.
• [15]NOODLEMAN L,BAERENDS E J.Electronic structure,magnetic properties,ESR,and optical spectra for 2-iron ferredoxin models by LCAO-X.alpha.valence bond theory[J].Journal of The American Chemical Society,1984,106(8):2316-2327.
• [16]NOODLEMAN L,PENG CY,CASE D A,et al.Orbital interactions,electron delocalization and spin coupling in iron-sulfur clusters[J].Coordination Chemistry Reviews,1995,144(2):199-244.
• [17]KO K C,SON S U,LEE S,et al.Diazaphenalenyl-containing spin sources designed by standardization of intramolecular magnetic interactions[J].Journal of Physical Chemistry B,2011,115(26):8401-8408.
• [18]YAMAGUCHI K,TAKAHARA Y,FUENO T,et al.Ab Initio MO calculations of effective exchange integrals between transition-metal ions via oxygen dianions:Nature of the copper-oxygen bonds and superconductivity[J].Japanese Journal of Applied Physics.1987,26(8):L1362-L1364.
• [19]YAMAGUCHI K,JENSEN F,DORIGO A,et al.A spin correction procedure for unrestricted Hartree-Fock and M?ller-Plesset wavefunctions for singlet diradicals and polyradicals[J].Chemical Physics Letters.1988,149(5-6):537-542.
• [20]FUKUI K,YONEZAWA T,SHINGU H.A molecular orbital theory of reactivity in aromatic hydrocarbons[J].Journal of Chemical Physics,1952,20(4):722-725.
• [21]AIHARA J I.Reduced HOMO-LUMO gap as an index of kinetic stability for polycyclic aromatic hydrocarbons[J].Journal of Physical Chemistry A,1999,103(37):7487-7495.
• [22]MANOLOPOULOS D E,MAY J C,DOWN S E.Theoretical studies of the fullerenes:C34 to C70[J].Chemical Physics Letters,1991,181(2-3):105-111.
• [23]BENDIKOV M,DUONG H M,Starkey Kyle,et al.Oligoacenes:Theoretical prediction of open-shell singlet diradical ground states[J].Journal of the American Chemical Society,2004,126(24):7416-7417.
• [24]DOEHNERT D,KOUTECKY J.Occupation numbers of natural orbitals as a criterion for biradical character.Different kinds of biradicals[J].Journal of The American Chemical Society,1980,102(6):1789-1796.
• [25]MARKOVIC S,DURDEVIC J,JEREMIC S,et al.Triplet fluoranthenes:Aromaticity versus unpaired electrons[J].Journal of Molecular Modeling,2011,17(4):805-810.
• [26]TRINDLE C,DATTA S N,MALLIK B.Phenylene coupling of methylene sites.The spin states of bis(X-methylene)-p-phenylenes and bis(chloromethylene)-m-phenylene[J].Journal of The American Chemical Society,1997,119(52):12947-12951.
• [27]KO K C,CHO D,LEE J Y.Systematic approach to design organic magnetic molecules:Strongly coupled diradicals with ethylene coupler[J].Journal of Physical Chemistry A,2012,116(25):6837-6844.