CN113831368A - 一种有机硅烷配体保护的混价十核锰簇合物及其制备方法 - Google Patents
一种有机硅烷配体保护的混价十核锰簇合物及其制备方法 Download PDFInfo
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- CN113831368A CN113831368A CN202110935055.1A CN202110935055A CN113831368A CN 113831368 A CN113831368 A CN 113831368A CN 202110935055 A CN202110935055 A CN 202110935055A CN 113831368 A CN113831368 A CN 113831368A
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- 239000011572 manganese Substances 0.000 title claims abstract description 61
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 52
- 150000001875 compounds Chemical class 0.000 title claims abstract description 48
- 150000001282 organosilanes Chemical class 0.000 title claims abstract description 41
- 239000003446 ligand Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 238000004729 solvothermal method Methods 0.000 claims abstract description 11
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 125000001424 substituent group Chemical group 0.000 claims abstract description 9
- 238000010992 reflux Methods 0.000 claims abstract description 7
- 239000003513 alkali Substances 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 4
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 claims description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 3
- 150000007529 inorganic bases Chemical class 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical group CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims description 3
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 2
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 150000007530 organic bases Chemical class 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims 1
- 229960001701 chloroform Drugs 0.000 claims 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims 1
- 239000000243 solution Substances 0.000 abstract description 5
- 238000010438 heat treatment Methods 0.000 abstract 1
- 239000012266 salt solution Substances 0.000 abstract 1
- 239000011259 mixed solution Substances 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 150000002696 manganese Chemical class 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000012546 transfer Methods 0.000 description 5
- -1 3-methoxy salicyloyl Chemical group 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- CUTSCJHLMGPBEJ-UHFFFAOYSA-N [N].CN(C)C=O Chemical compound [N].CN(C)C=O CUTSCJHLMGPBEJ-UHFFFAOYSA-N 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 230000005389 magnetism Effects 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 3
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 3
- 239000011565 manganese chloride Substances 0.000 description 3
- 235000002867 manganese chloride Nutrition 0.000 description 3
- 229940099607 manganese chloride Drugs 0.000 description 3
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- BJMBNXMMZRCLFY-UHFFFAOYSA-N [N].[N].CN(C)C=O Chemical compound [N].[N].CN(C)C=O BJMBNXMMZRCLFY-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 229940071125 manganese acetate Drugs 0.000 description 2
- 229910001437 manganese ion Inorganic materials 0.000 description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 238000006884 silylation reaction Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 description 1
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000013500 data storage Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- SJFIRQVWOJTTCR-UHFFFAOYSA-L dichloromanganese;oxolane Chemical compound Cl[Mn]Cl.C1CCOC1.C1CCOC1 SJFIRQVWOJTTCR-UHFFFAOYSA-L 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000010365 information processing Effects 0.000 description 1
- DTMCOMZUESDMSN-UHFFFAOYSA-N lithium;trimethylsilicon Chemical compound [Li][Si](C)(C)C DTMCOMZUESDMSN-UHFFFAOYSA-N 0.000 description 1
- QWDJLDTYWNBUKE-UHFFFAOYSA-L magnesium bicarbonate Chemical compound [Mg+2].OC([O-])=O.OC([O-])=O QWDJLDTYWNBUKE-UHFFFAOYSA-L 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
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Abstract
本发明涉及一种有机硅烷配体保护的混价十核锰簇合物及其制备方法,制备过程包括步骤如下:先将碱溶于醇类溶剂,然后加入含有取代基的三烷氧基硅烷,回流反应,发生预水解缩聚,得到预聚体;然后加入二价锰的金属盐溶液,将混合物溶液转移至反应釜中加热,进行溶剂热反应,生成有机硅烷保护的混价十核锰簇合物。本发明还提供上述方法制备得到的混价十核锰簇合物。本发明是通过溶剂热的方法实现的,反应条件易于控制,得到的锰簇合物结构明确、纯度较高,可以直接进行应用,具有巨大的应用前景。
Description
技术领域
本发明涉及一种有机硅烷配体保护的混价十核锰簇合物及其制备方法,属于纳米材料合成技术领域。
背景技术
混价锰簇合物由于具有有趣的电子结构、杰出的磁性(单分子磁体)和催化性能引起了研究者的广泛关注。自从20世纪90年代第一个单分子磁体Mn12被成功制备以来,一系列的不同配体保护的多核锰簇被成功制备和分离,如羧基、β-二酮,吡啶-醇类等。有机硅烷通过水解缩聚可以形成多种低聚形式[RSiO1.5]n(n=1,2,4.6等),这些低聚未形成全封闭结构的有机硅烷具有多个氧配位点,已被证实是一类优良的多齿配体,可以很好的保护并稳定多核金属离子,且制备的多核金属簇合物表现出多变的结构和优良的磁性以及催化性能。随着科学家们不断深入的研究,越来越多的锰簇合物被制备出来,预期在数据存储、量子计算、高密度信息处理、自旋电子学及磁性制冷等诸多领域有潜在的应用。
国外文献(Z.Anorg.Allg.Chem.,2008,634,2819)报道,F.T.Edelmann等人首次制备了低聚有机硅烷[Si7]保护的Mn4簇合物。将制备好的硅醇前体(Si7)和二(三甲基硅)氮化锂的乙醚溶液基二(三甲基硅)胺的四氢呋喃溶液混合后,搅拌过夜,然后加入二(四氢呋喃) 氯化锰,继续搅拌24小时,真空去除溶剂,用乙醚提取,得到浅棕色的Mn4簇合物晶体。该报道为首例有机硅保护的锰簇合物,尽管产率较高(81%),然而整个实验依赖于无水无氧的惰性气氛。
国外文献(Russ.Chem.Bull.,Int.Ed.,2011,60,1762)报道,利用三乙氧基硅烷为前体,与水和乙醇混合搅拌20分钟后,加入氢氧化钠,将反应加热至35-40度,加入无水氯化锰的乙醇溶液,回流2小时后热过滤得到有机硅烷保护的八核锰簇合物,然而产率仅有12%。
国外文献(Inorg.Chem.,2021,60,2866)报道,将二(四氢呋喃)二(三甲基硅)氮化镁的吡啶和甲苯的混合溶液加入三硅醇[Si7]的吡啶和甲苯的混合溶液中,再加入一定量戊烷,然后将混合物置于-40℃保持72小时,可以得到74-78%左右的Mn3和Mn4簇合物。然而其反应须在氮气氛围下,且为极低温反应。
国内尚未发现有机硅保护的锰簇合物的相关报道。对于其他有机配体保护的锰簇合物的研究相对较多。例如:中国专利(CN104505210 A)公开了一种N,N’-(2,6-吡啶二甲酰基)-二水杨酰肼和乙酰丙酮共保护的混价锰簇合物(Mn3),对其精确结构和磁性做了相关表征。中国专利(CN 104530133 A)公开了一种利用溶剂热法,由茚三酮-2-重氮基-1-(3-甲氧基水杨酰基)酰腙、3-甲氧基水杨酰肼和N-甲基二乙醇胺共保护的Mn6簇合物,对其结构和磁性进行了相关表征。中国专利(CN 105753797 A)公开了一种含硫三氮唑配体保护的高核Mn24簇合物,对其结构进行了相关表征。中国专利(CN 107056647 A)公开了一种利用溶剂热法,N,N’- 二(水杨酰基)-(E)-丁烯二酰肼配体保护的Mn16簇合物,对其结构、磁性和CO2吸附性能进行了相关表征。
综合分析国内外研究,发现目前有机硅烷作为配体保护的金属簇合物的研究相对较少,有机硅烷保护的锰簇合物更加稀少,且目前已报道的有基硅烷保护的锰簇合物均是在氮气等惰性气氛下获得,有时还需要极低温等较为苛刻的条件,所以急需要对有机硅烷保护的锰簇合物制备技术进行优化和改进,研究一种制备条件温和的技术路线。
发明内容
针对国内外在有机硅烷保护的锰簇合物的制备中的不足,本发明提出一种利用溶剂热法在大气环境下制备有机硅烷保护的混价锰簇合物的方法,具有反应条件简单、成本低、收率高、重复性好、且结构可控的特点,具有广阔的应用前景。且该方法还可扩展到有机硅烷保护的其他金属簇合物的制备,这为有机硅在簇合物制备领域的广阔应用提供了便利的方法。通过改变反应原料的基团种类,可以根据不同需求获得种类更为丰富的锰簇合物,具有突出的便利性。
发明概述
本发明提供的一种有机硅烷配体保护的混价十核锰簇合物及其制备方法,是通过溶剂热的方法得到的,反应条件易于控制,得到的锰簇合物结构明确、纯度较高,具有巨大的应用前景。所制备的锰簇合物可以直接进行应用,还可扩展到有机硅烷保护的其他过渡金属簇合物的制备,也可对有机硅烷的R’基团进行修饰和改性,获得种类和性能更加丰富多样的锰簇合物,有望应用在分子磁体及催化等领域。
发明详述
本发明的技术方案如下:
一种有机硅烷配体保护的混价十核锰簇合物的制备方法,包括步骤如下:
先将三烷氧基硅烷溶于醇类溶剂,加入适量碱调节pH值,然后回流一定时间,发生预水解缩聚,得到预聚体,然后加入二价锰离子金属盐的乙腈和氮氮二甲基甲酰胺混合溶液,将其转移至反应釜中,冷却到室温,即可得到有机硅烷保护的混价十核锰簇合物。
本发明的合成技术路线如下所示:
其中:R`为苯基或甲基。n为整数(1,2,3或4)。
根据本发明,上述的醇类溶剂是指能够溶解烷氧基硅烷的醇类化合物,优选甲醇、乙醇、丙醇、正丁醇,进一步优选甲醇和乙醇。
根据本发明,上述的碱是指广义的碱性物质,包括无机碱和有机碱,优选氢氧化钾、氢氧化钠、氢氧化锂、氢氧化铯、四甲基氢氧化铵,进一步优选氢氧化钠和四甲基氢氧化铵;
优选的,调节pH值为碱性环境,进一步优选调节pH为8-9。
根据本发明,上述的含有取代基的三烷氧基硅烷为市售的各类三烷氧基硅烷,优选甲基三乙氧基硅烷、甲基三甲氧基硅烷、苯基三甲氧基硅烷,苯基三乙氧基硅烷、氨丙基三乙氧基硅烷、氨丙基三甲氧基硅烷及其苯基上含有取代基的三烷氧基硅烷的衍生物,进一步优选苯基三乙氧基硅烷、甲基三乙氧基硅烷和氨丙基三乙氧基硅烷。
根据本发明,优选的,含有取代基的三烷氧基硅烷、碱和溶剂的摩尔比为1:(1.6-2): (10-100)。
根据本发明,上述的回流温度为使体系产生回流的温度,随溶剂的不同而变化。
根据本发明,上述的回流时间为3-8小时,优选4-5小时。
根据本发明,上述的溶剂热反应的反应温度为120-200℃,进一步优选120-140℃。
根据本发明,上述的溶剂热反应的反应时间为10-15小时,进一步优选13-15小时。
根据本发明,还提供上述方法制备得到的有机硅烷配体保护的混价十核锰簇合物。
本发明未详尽说明的,均按现有技术。
本发明的原理:
本发明通过巧妙地设计反应体系和顺序,结合溶剂的优选,在大气氛围下短时、高效地制备了有机硅烷保护的混价十核锰簇合物。该反应体系不需要在低温和惰性气体保护下进行,而是通过调节溶液pH值和温度控制硅氧烷前体自身的水解和缩聚形成低聚硅氧烷配体,形成的低聚硅氧烷配体在常温下即可与金属锰离子自组装形成簇合物,这为高效制备有机硅烷保护的金属团簇提供了一个崭新的途径。本发明制备工序简单、重复性好、收率高、创新性强。
本发明一种有机硅烷配体保护的混价十核锰簇合物的制备方法具有制备工艺简单、易于工业生产的特点,收率高、可控性好,取得了意想不到的效果,具有突出的创新性。制备的有机硅烷保护的混价锰簇合物可以直接使用,也可以通过对有机硅氧烷进一步的修饰和改性获得种类更加丰富、性能更加优良的簇合物,合成方法便利、创新性强、应用前景广阔。
本发明的有益效果:
1、本发明有机硅烷配体保护的混价十核锰簇合物具有制备工艺简单、易于工业生产的特点,反应条件温和,无需惰性气氛,重现性好,取得了意想不到的效果,具有突出的创新性。
2、本发明方法产物收率高,可达71%,反应高效,10-20小时即可完成反应。
3、本发明有机硅烷配体保护的混价十核锰簇合物可以直接使用合成方法便利、应用前景广阔。
附图说明
图1为本发明实施例1制备的有机硅烷配体保护的混价十核锰簇合物的单晶衍射图。
图2为本发明试验例2中室温下催化苯甲醛硅氰化反应产物的核磁氢谱图。
具体实施方式
下面通过具体实施例对本发明做进一步说明,但不限于此。
实施例中所用原料均为常规市购原料或按照参考文献方法合成得到。
实施例1
先将4克苯基三乙氧基硅烷溶于50毫升乙醇,然后加入NaOH调节pH值为8-9,在80温度下回流4小时,发生预水解缩聚,得到预聚体,然后加入醋酸锰(2克)的乙腈和氮氮二甲基甲酰胺的混合溶液(250毫升,体积比3/2)将其转移至反应釜中,反应温度为120度,反应时间为12小时),实验结束后反应釜冷却至室温,可得到有机硅烷保护的十核锰簇合物。收率71%。
实施例2
先将4.5克苯基三甲氧基硅烷溶于60毫升乙醇,然后加入NaOH调节pH值为8-9,在70温度下回流5小时,发生预水解缩聚,得到预聚体,然后加入氯化锰(2.5克)的乙腈和氮氮二甲基甲酰胺的混合溶液(200毫升,体积比3/2)将其转移至反应釜中,反应温度为130 度,反应时间为14小时),实验结束后反应釜冷却至室温,可得到有机硅烷保护的十核锰簇合物。收率66%。
实施例3
先将6克苯基三乙氧基硅烷溶于40毫升丙醇,然后加入NaOH调节pH值为8-9,在100温度下回流4小时,发生预水解缩聚,得到预聚体,然后加入醋酸锰(3克)的乙腈和氮氮二甲基甲酰胺的混合溶液(150毫升,体积比3/2)将其转移至反应釜中,反应温度为140度,反应时间为14小时),实验结束后反应釜冷却至室温,可得到有机硅烷保护的十核锰簇合物。收率69%。
实施例4
先将6克苯基三甲氧基硅烷溶于40毫升正丁醇,然后加入NaOH调节pH值为8-9,在100温度下回流5小时,发生预水解缩聚,得到预聚体,然后加入硫酸锰(3.5克)的乙腈和氮氮二甲基甲酰胺的混合溶液(200毫升,体积比3/2)将其转移至反应釜中,反应温度为120度,反应时间为12小时),实验结束后反应釜冷却至室温,可得到有机硅烷保护的十核锰簇合物。收率57%。
实施例5
先将4克苯基三乙氧基硅烷溶于50毫升乙醇,然后加入NaOH调节pH值为8-9,在80温度下回流4小时,发生预水解缩聚,得到预聚体,然后加入氯化锰(2.5克)的乙腈和氮氮二甲基甲酰胺的混合溶液(300毫升,体积比3/2)将其转移至反应釜中,反应温度为130度,反应时间为13小时),实验结束后反应釜冷却至室温,可得到有机硅烷保护的十核锰簇合物。收率65%。
试验例1
将实施例1制备的有机硅烷保护的混价锰簇合物晶体进行单晶衍射表征,如图1所示,结构测试结果表明,本发明的有机硅烷保护的锰簇得到了成功制备,该反应条件相对温和,易于控制,适于制备不同取代基的有机硅烷保护的锰簇,相比于文献报道的惰性气氛合成方法,该方法具有较大的创新性,有望应用于分子磁体和催化等领域。
试验例2
将实施例1制备的有机硅烷保护的混价锰簇合物晶体,室温下进行催化苯甲醛硅氰化反应性能测试,利用核磁氢谱对反应产物进行表征,如图2所示。图2催化测试结果表明,本发明的有机硅烷保护的锰簇可以在室温下催化苯甲醛硅氰化反应,催化剂用量为底物的 1mol%,反应12h转化率约为96%。
Claims (10)
1.一种有机硅烷配体保护的混价十核锰簇合物的制备方法,包括步骤如下:
先将碱溶于醇类溶剂,然后加入含有取代基的三烷氧基硅烷,回流反应,发生预水解缩聚,得到预聚体;然后将预聚体和二价锰的溶液混合,再转移至反应釜中进行溶剂热反应,生成有机硅烷配体保护的混价十核锰簇合物。
2.根据权利要求1所述的有机硅烷配体保护的混价十核锰簇合物的制备方法,其特征在于,所述的醇类溶剂为甲醇、乙醇、丙醇或正丁醇。
3.根据权利要求1所述的有机硅烷配体保护的混价十核锰簇合物的制备方法,其特征在于,所述的碱是无机碱或有机碱;优选无机碱,进一步优选氢氧化钾、氢氧化钠。
4.根据权利要求1所述的有机硅烷配体保护的混价十核锰簇合物的制备方法,其特征在于,所述的含有取代基的三烷氧基硅烷为甲基三乙氧基硅烷、甲基三甲氧基硅烷、氨丙基三乙氧基硅烷、氨丙基三甲氧基硅烷、苯基三甲氧基硅烷,苯基三乙氧基硅烷及其苯基上含有取代基的三烷氧基硅烷的衍生物。
5.根据权利要求1所述的有机硅烷配体保护的混价十核锰簇合物的制备方法,其特征在于,含有取代基的三烷氧基硅烷、碱和溶剂的摩尔比为1:(1.6-2):(10-100)。
6.根据权利要求1所述的有机硅烷配体保护的混价十核锰簇合物的制备方法,其特征在于,所述的回流反应时间为3-8小时,优选4-5小时。
7.根据权利要求1所述的有机硅烷配体保护的混价十核锰簇合物的制备方法,其特征在于,所述的溶解二价锰的溶剂为乙腈、四氢呋喃、三氯甲烷、二氯甲烷、N,N’-二甲基甲酰胺及上述溶剂的混合物,优选乙腈或N,N’-二甲基甲酰胺。
8.根据权利要求1所述的有机硅烷配体保护的混价十核锰簇合物的制备方法,其特征在于,所述的溶剂热反应的反应温度为120-200℃,优选120-140℃。
9.根据权利要求1所述的有机硅烷配体保护的混价十核锰簇合物的制备方法,其特征在于,所述的溶剂热反应的时间为10-15小时,优选13-15小时。
10.权利要求1所述的制备方法制备得到的有机硅烷配体保护的混价十核锰簇合物。
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