[发明专利]磁性材料HN(C2H5)3·[Co4Na3(heb)6(N3)6]及合成方法

权利要求书

1.一种磁性材料HN(C₂H₅)₃·[Co₄Na₃(heb)₆(N₃)₆]，其特征在于HN(C₂H₅)₃·[Co₄Na₃(heb)₆(N₃)₆]具有优良的磁学特性，其分子式为：C₆₀H₇₁N₁₉Na₃Co₄O₁₈，分子量为：1651.05，其中Hheb为3-乙氧基-2-羟基苯甲醛，晶体结构数据见表一，键长键角数据见表二；HN(C₂H₅)₃·[Co₄Na₃(heb)₆(N₃)₆]的磁学性质：(1)分子内钴离子间存在铁磁交换，其整体表现为铁磁性；(2)HN(C₂H₅)₃·[Co₄Na₃(heb)₆(N₃)₆]在室温下χ_MT为12.53cm³Kmol^-1，随着温度降低，χ_MT逐渐升高，至14K达到最大值20.08cm³Kmol^-1，随后急剧降至2K时的8.38cm³Kmol-¹；且χ_M^–1-T曲线遵从居里-韦斯定律，对其拟合得到韦斯常数为5.00K，居里常数为12.56cm³Kmol^–1；大而正的韦斯常数及χ_MT-T曲线趋势均暗示分子内钴离子间存在铁磁交换，其整体表现为铁磁性；

所述HN(C₂H₅)₃·[Co₄Na₃(heb)₆(N₃)₆]的合成方法具体步骤为：

将0.166克分析纯3-乙氧基-2-羟基苯甲醛溶于4-8毫升分析纯甲醇4-8毫升分析纯乙腈的混合溶液中，再依次加入0.36-0.72g分析纯六水合高氯酸钴和0.065-0.13g分析纯叠氮化钠，并搅拌10分钟使溶液混合均匀后加入分析纯三乙胺调节至pH＝5.5，继续搅拌20分钟后，将所制得的混合液静置于室温下，30分钟后得到红色条状晶体，过滤，并用分析纯甲醇洗涤干净，于空气中晾干后得到产品HN(C₂H₅)₃·[Co₄Na₃(heb)₆(N₃)₆]；

表一HN(C₂H₅)₃·[Co₄Na₃(heb)₆(N₃)₆]·(CH₃OH)的晶体学参数

表二HN(C₂H₅)₃·[Co₄Na₃(heb)₆(N₃)₆]·(CH₃OH)的键长和键角(°)

C1-O11.286(7)C46-C471.412(8)C36-H360.9300C1-C21.410(9)C46-C511.424(8)C37-O131.293(7)

C1-C61.417(9)C47-C541.427(9)C37-C381.404(8)C2-C31.401(10)C47-C481.431(9)C37-C421.437(8)C2-C91.431(10)C48-C491.351(10)C38-C451.414(9)C3-C41.349(12)C48-H480.9300C38-C391.416(9)C3-H30.9300C49-C501.370(10)C39-C401.353(11)C4-C51.399(11)C49-H490.9300C39-H390.9300C4-H40.9300C50-C511.388(8)C40-C411.375(10)C5-C61.363(9)C50-H500.9300C40-H400.9300C5-H50.9300C51-O181.363(7)Na2-O122.454(5)C6-O31.387(7)C52-O181.427(7)C30-C311.373(11)C7-O31.445(8)C52-C531.490(10)C57-H57B0.9700C7-C81.462(11)C52-H52A0.9700C14-C151.376(10)C7-H7A0.9700C52-H52B0.9700Na3-O72.247(4)C7-H7B0.9700C53-H53A0.9600Na3-O42.266(4)C8-H8A0.9600C53-H53B0.9600Na3-O92.390(5)C8-H8B0.9600C53-H53C0.9600Na3-O62.458(6)C8-H8C0.9600C54-O171.231(8)C45-H450.9300C9-O21.222(9)C54-H540.9300C46-O161.285(6)C9-H90.9300C55-C561.40(2)C41-C421.371(9)C10-O41.291(7)C55-H55A0.9600C41-H410.9300C10-C111.408(9)C55-H55B0.9600C42-O151.381(7)C10-C151.417(9)C55-H55C0.9600C43-O151.424(7)C11-C181.429(11)C56-N191.446(18)C43-C441.497(10)C11-C121.438(11)C56-H56A0.9700C43-H43A0.9700C12-C131.328(13)C56-H56B0.9700C43-H43B0.9700C12-H120.9300C57-N191.489(10)C44-H44A0.9600C13-C141.391(13)C57-C581.563(10)C44-H44B0.9600C13-H130.9300C57-H57A0.9700C44-H44C0.9600C14-H140.9300C58-H58A0.9600Co2-O12.025(4)C15-O61.345(8)C58-H58B0.9600Co2-O42.043(4)C16-C171.352(14)C58-H58C0.9600Co2-O22.097(4)C16-O61.448(11)C59-C601.367(17)Co2-O52.106(5)C16-H16A0.9700C59-N191.410(16)Co3-O132.021(4)C16-H16B0.9700C59-H59A0.9700Co3-O162.025(4)C17-H17A0.9600C59-H59B0.9700Co3-O142.078(4)C17-H17B0.9600C60-H60A0.9600Co3-O172.114(4)C17-H17C0.9600C60-H60B0.9600Co4-O102.029(4)C18-O51.209(9)C60-H60C0.9600C45-O141.242(8)C18-H180.9300N1-N21.179(7)Co4-O72.040(4)C19-O71.281(7)N1-Co22.143(4)Co4-O112.081(4)C19-C201.412(9)N1-Co12.158(4)Co4-O82.099(4)C19-C241.424(9)N1-Na32.548(5)Na2-O132.260(4)C30-H300.9300N2-N31.143(8)Na2-O102.275(4)C20-C211.413(9)C32-C331.350(9)Na2-O152.427(5)C20-C271.412(10)N4-N51.170(6)C31-C321.386(11)C21-C221.347(12)N4-Co12.165(4)N16-N171.196(6)C21-H210.9300N4-Co32.186(4)N16-Co32.155(4)C22-C231.375(12)N4-Na12.524(4)N16-Co12.178(4)C22-H220.9300N5-N61.144(8)N16-Na22.525(4)C23-C241.389(9)C36-O111.233(8)N17-N181.132(7)C23-H230.9300N7-N81.182(6)N19-H19A0.9137C24-O91.366(8)N7-Co42.158(4)Na1-O162.267(4)C25-O91.431(9)N7-Co12.175(4)Na1-O12.277(4)C25-C261.452(12)N7-Na22.498(5)Na1-O182.402(4)C25-H25A0.9700N8-N91.137(8)Na1-O32.466(5)C25-H25B0.9700N10-N111.195(6)C32-H32A0.9700C26-H26A0.9600N10-Co22.145(4)C32-H32B0.9700C26-H26B0.9600N10-Co12.166(4)C33-O121.390(7)C26-H26C0.9600N10-Na12.539(5)C34-O121.424(7)C27-O81.249(8)N11-N121.141(7)C34-C351.506(11)C27-H270.9300N13-N141.180(6)C34-H34A0.9700C28-O101.294(7)N13-Co12.142(4)C34-H34B0.9700C28-C291.419(8)N13-Co42.175(4)C35-H35A0.9600C28-C331.422(8)N13-Na32.540(5)C35-H35B0.9600C29-C301.420(9)N14-N151.141(7)C35-H35C0.9600C29-C361.421(9)C31-H310.9300  O1-C1-C2123.7(6)O18-Na1-N4140.59(16)H60A-C60-H60C109.5O1-C1-C6120.4(5)O3-Na1-N499.41(16)H60B-C60-H60C109.5C2-C1-C6115.9(6)O16-Na1-N1091.88(15)N2-N1-Co2123.6(4)C3-C2-C1120.9(7)O1-Na1-N1074.29(15)N2-N1-Co1131.2(4)C3-C2-C9117.1(7)O18-Na1-N1097.31(16)Co2-N1-Co199.27(17)C1-C2-C9122.0(7)O3-Na1-N10140.54(16)N2-N1-Na3102.7(4)C4-C3-C2121.3(8)N4-Na1-N1075.03(14)Co2-N1-Na392.05(17)C4-C3-H3119.3O14-C45-C38128.8(6)Co1-N1-Na397.26(17)C2-C3-H3119.3O18-C52-H52B109.9N3-N2-N1176.3(8)

C3-C4-C5119.2(8)O18-C52-H52A109.9O10-Co4-N787.90(15)C3-C4-H4120.4C53-C52-H52A109.9O7-Co4-N795.59(16)C5-C4-H4120.4C40-C39-H39119.5O11-Co4-N7169.56(17)C6-C5-C4120.6(8)C38-C39-H39119.5O8-Co4-N794.85(17)C6-C5-H5119.7O10-Co4-O1186.86(16)O10-Co4-N1394.37(16)C4-C5-H5119.7O7-Co4-O1189.88(17)O7-Co4-N1387.39(15)C5-C6-O3124.7(7)O10-Co4-O892.51(17)O11-Co4-N1390.71(17)C5-C6-C1122.0(7)O7-Co4-O886.02(16)O8-Co4-N13171.65(18)O3-C6-C1113.3(6)O11-Co4-O894.39(18)N7-Co4-N1380.70(15)O3-C7-C8108.8(7)N19-C59-H59B105.8O10-Co4-O7176.31(15)O3-C7-H7A109.9H59A-C59-H59B106.2O15-C43-H43A110.2C8-C7-H7A109.9C59-C60-H60A109.5C43-C44-H44A109.5O3-C7-H7B109.9C59-C60-H60B109.5N5-N4-Co1130.6(4)C8-C7-H7B109.9H60A-C60-H60B109.5N5-N4-Co3123.0(4)H7A-C7-H7B108.3C57-C58-H58A109.5Co1-N4-Co398.60(16)C7-C8-H8A109.5C57-C58-H58B109.5N5-N4-Na1105.0(4)C7-C8-H8B109.5H58A-C58-H58B109.5Co1-N4-Na197.33(16)H8A-C8-H8B109.5C57-C58-H58C109.5Co3-N4-Na193.07(14)C7-C8-H8C109.5H58A-C58-H58C109.5N6-N5-N4176.3(7)H8A-C8-H8C109.5H58B-C58-H58C109.5O15-C42-C37113.4(5)H8B-C8-H8C109.5C60-C59-N19125.9(16)O14-Co3-O1792.12(18)O2-C9-C2130.6(7)C60-C59-H59A105.8O13-Co3-N1687.04(15)O2-C9-H9114.7N19-C59-H59A105.8O16-Co3-N1694.39(16)C2-C9-H9114.7C60-C59-H59B105.8O14-Co3-N16171.28(16)O4-C10-C11123.1(6)C58-C57-H57A107.1O17-Co3-N1694.70(17)O4-C10-C15118.5(6)N19-C57-H57B107.1O13-Co3-N493.79(16)C11-C10-C15118.4(6)C58-C57-H57B107.1O16-Co3-N486.80(15)C10-C11-C18122.5(7)H57A-C57-H57B106.8O14-Co3-N492.73(17)C10-C11-C12118.7(8)O13-Na2-O10165.56(17)O17-Co3-N4171.80(17)C18-C11-C12118.8(7)O13-Na2-O1567.32(14)N16-Co3-N481.15(15)C13-C12-C11121.7(9)O10-Na2-O15123.91(16)O15-C43-C44107.4(6)C13-C12-H12119.2O13-Na2-O12120.08(16)N8-N7-Co4124.7(4)C11-C12-H12119.2O10-Na2-O1267.31(14)N8-N7-Co1126.9(4)C12-C13-C14119.6(9)O15-Na2-O12108.69(17)Co4-N7-Co198.88(17)C12-C13-H13120.2O13-Na2-N794.67(16)N8-N7-Na2109.1(4)C14-C13-H13120.2O10-Na2-N774.88(15)Co4-N7-Na293.25(16)C15-C14-C13121.8(9)O15-Na2-N7101.38(16)Co1-N7-Na295.48(15)C15-C14-H14119.1O12-Na2-N7140.52(16)N9-N8-N7179.1(9)C13-C14-H14119.1O13-Na2-N1673.69(15)N11-N10-Co2122.7(4)O6-C15-C14125.3(8)O10-Na2-N1694.03(15)N11-N10-Co1131.2(4)O6-C15-C10114.9(6)O15-Na2-N16140.80(16)N10-Co1-N1694.73(16)C14-C15-C10119.8(8)O12-Na2-N1693.91(15)N7-Co1-N1692.44(15)C17-C16-O6112.0(10)N7-Na2-N1677.45(14)C1-O1-Co2130.6(4)C17-C16-H16A109.2O16-Co3-O1491.45(16)C1-O1-Na1122.4(4)O6-C16-H16A109.2O13-Co3-O1793.05(17)Co2-O1-Na1104.30(17)C17-C16-H16B109.2O16-Co3-O1786.47(16)C9-O2-Co2124.9(5)O6-C16-H16B109.2O13-Co3-O16178.52(16)C6-O3-C7116.8(6)H16A-C16-H16B107.9O13-Co3-O1487.18(15)C6-O3-Na1115.6(4)C16-C17-H17A109.5C55-C56-H56B108.9C7-O3-Na1125.4(4)C16-C17-H17B109.5N19-C56-H56B108.9C10-O4-Co2130.6(4)H17A-C17-H17B109.5H56A-C56-H56B107.7C10-O4-Na3122.6(4)C16-C17-H17C109.5N19-C57-C58121.0(11)Co2-O4-Na3103.52(18)H17A-C17-H17C109.5N19-C57-H57A107.1Co2-N10-Co198.92(17)H17B-C17-H17C109.5C56-C55-H55C109.5N11-N10-Na1104.7(4)O5-C18-C11130.0(7)H55A-C55-H55C109.5Co2-N10-Na192.70(16)O5-C18-H18115.0H55B-C55-H55C109.5Co1-N10-Na196.87(17)C11-C18-H18115.0C55-C56-N19113.4(16)N12-N11-N10177.7(7)O7-C19-C20124.3(6)C55-C56-H56A108.9N14-N13-Co1129.9(4)O7-C19-C24118.3(6)N19-C56-H56A108.9N14-N13-Co4124.0(4)C20-C19-C24117.4(6)N13-Co1-N1094.26(16)Co1-N13-Co499.36(17)O15-C43-H43B110.2N1-Co1-N1080.50(17)N14-N13-Na3103.5(4)C44-C43-H43B110.2N4-Co1-N1090.76(16)Co1-N13-Na397.92(17)H43A-C43-H43B108.5N13-Co1-N781.06(16)Co4-N13-Na392.41(15)C19-C20-C21120.7(7)N1-Co1-N792.73(16)N15-N14-N13176.0(7)C19-C20-C27122.2(6)O7-Na3-O4164.91(17)C18-O5-Co2125.7(5)C21-C20-C27117.2(7)O7-Na3-O968.12(16)C15-O6-C16116.6(7)C22-C21-C20120.5(8)O4-Na3-O9122.44(18)C15-O6-Na3115.7(4)C22-C21-H21119.8O7-Na3-O6123.4(18)C16-O6-Na3125.8(5)C20-C21-H21119.8O4-Na3-O666.65(17)C19-O7-Co4131.1(4)C21-C22-C23120.1(7)O9-Na3-O6105.18(19)C19-O7-Na3122.4(4)C21-C22-H22119.9O7-Na3-N1374.72(14)Co4-O7-Na3105.42(16)C23-C22-H22119.9O4-Na3-N1393.26(15)C27-O8-Co4126.1(5)C22-C23-C24122.0(8)O9-Na3-N13142.51(18)C24-O9-C25119.4(6)C22-C23-H23119.0O6-Na3-N1399.03(18)C24-O9-Na3116.0(4)C24-C23-H23119.0O7-Na3-N192.58(16)O14-C45-H45115.6

O9-C24-C23126.3(7)O4-Na3-N175.06(16)C38-C45-H45115.6O9-C24-C19114.4(5)O9-Na3-N1102.45(18)N17-N16-Co3121.6(4)C23-C24-C19119.3(7)O6-Na3-N1140.69(17)N17-N16-Co1127.5(4)O9-C25-C26110.0(7)N13-Na3-N174.00(15)Co3-N16-Co199.16(17)O9-C25-H25A109.7C42-C41-C40120.5(7)N17-N16-Na2112.6(3)C26-C25-H25A109.7C42-C41-H41119.7Co3-N16-Na293.46(16)O9-C25-H25B109.7C40-C41-H41119.7Co1-N16-Na294.63(15)C26-C25-H25B109.7C59-C60-H60C109.5N18-N17-N16176.5(7)H25A-C25-H25B108.2O16-C46-C47124.7(5)C59-N19-C56111.4(12)C25-C26-H26A109.5O16-C46-C51118.2(5)C25-O9-Na3124.5(5)C25-C26-H26B109.5C44-C43-H43A110.2C28-O10-Co4129.0(4)H26A-C26-H26B109.5C53-C52-H52B109.9C28-O10-Na2121.4(3)C25-C26-H26C109.5C41-C42-O15125.7(6)Co4-O10-Na2103.92(17)H26A-C26-H26C109.5C41-C42-C37120.9(6)C36-O11-Co4126.4(4)H26B-C26-H26C109.5C39-C40-C41120.6(8)C33-O12-C34117.3(5)O8-C27-C20129.6(6)C39-C40-H40119.7C33-O12-Na2115.3(3)O8-C27-H27115.2C41-C40-H40119.7C34-O12-Na2124.1(4)C20-C27-H27115.2N4-Co1-N794.37(16)C37-O13-Co3130.0(4)O10-C28-C29123.0(5)N10-Co1-N7171.75(16)C37-O13-Na2123.9(3)O10-C28-C33120.1(5)N13-Co1-N1694.92(16)O1-Na1-N493.01(15)C29-C28-C33116.9(6)N1-Co1-N16172.83(16)C59-N19-C57121.5(12)C28-C29-C30119.7(6)N4-Co1-N1681.10(15)C56-N19-C57106.1(12)C28-C29-C36123.6(6)O2-Co2-O597.26(19)C59-N19-H19A104.8C30-C29-C36116.7(7)O1-Co2-N195.31(17)C56-N19-H19A114.3C31-C30-C29120.5(8)O4-Co2-N189.26(16)C57-N19-H19A98.4C31-C30-H30119.8O2-Co2-N190.63(18)O16-Na1-O1163.36(16)C29-C30-H30119.8O5-Co2-N1170.63(19)O16-Na1-O1867.44(14)C30-C31-C32119.8(8)O1-Co2-N1088.66(16)O1-Na1-O18122.62(17)C30-C31-H31120.1O4-Co2-N1095.13(17)O16-Na1-O3124.77(17)C32-C31-H31120.1O2-Co2-N10170.44(19)O1-Na1-O366.94(16)C33-C32-C31121.1(7)O5-Co2-N1091.24(17)Co3-O13-Na2105.80(17)C33-C32-H32A107.1N1-Co2-N1081.32(17)C45-O14-Co3126.6(4)C31-C32-H32A107.1O1-Co2-O4174.47(16)C42-O15-C43115.8(5)C33-C32-H32B107.1O1-Co2-O286.97(18)C42-O15-Na2117.0(3)C31-C32-H32B107.1O4-Co2-O289.87(18)C43-O15-Na2126.7(4)H32A-C32-H32B106.8O1-Co2-O590.17(19)C46-O16-Co3130.6(4)C32-C33-O12124.7(6)O4-Co2-O585.73(18)C46-O16-Na1123.0(4)C32-C33-C28122.0(7)O1-Co2-O4174.47(16)Co3-O16-Na1105.80(15)O12-C33-C28113.2(5)N13-Co1-N190.80(17)C54-O17-Co3126.6(4)O12-C34-C35108.4(7)N13-Co1-N4173.84(16)C51-O18-C52117.9(5)O12-C34-H34A110.0N1-Co1-N493.54(16)C51-O18-Na1117.0(3)C35-C34-H34A110.0C56-C55-H55A109.5C52-O18-Na1125.1(4)O12-C34-H34B110.0C56-C55-H55B109.5O18-Na1-O3109.27(17)C35-C34-H34B110.0H55A-C55-H55B109.5O16-Na1-N474.15(14)H34A-C34-H34B108.4H52A-C52-H52B108.3C47-C46-C51117.2(5)C34-C35-H35A109.5C52-C53-H53A109.5C46-C47-C54122.6(6)C34-C35-H35B109.5C52-C53-H53B109.5C46-C47-C48120.0(6)H35A-C35-H35B109.5H53A-C53-H53B109.5C54-C47-C48117.4(6)C34-C35-H35C109.5C52-C53-H53C109.5C49-C48-C47120.6(7)H35A-C35-H35C109.5H53A-C53-H53C109.5C49-C48-H48119.7H35B-C35-H35C109.5H53B-C53-H53C109.5C47-C48-H48119.7O11-C36-C29128.0(7)O17-C54-C47128.5(6)C48-C49-C50120.4(6)O11-C36-H36116.0O17-C54-H54115.8C48-C49-H49119.8C29-C36-H36116.0C47-C54-H54115.8C50-C49-H49119.8O13-C37-C38124.7(5)C49-C50-H50119.3C49-C50-C51121.4(7)O13-C37-C42118.2(5)C51-C50-H50119.3C43-C44-H44B109.5C38-C37-C42117.1(6)O18-C51-C50125.2(6)H44A-C44-H44B109.5C37-C38-C45122.6(6)O18-C51-C46114.3(5)C43-C44-H44C109.5C37-C38-C39119.6(6)C50-C51-C46120.4(6)H44A-C44-H44C109.5C45-C38-C39117.7(6)O18-C52-C53109.0(6)H44B-C44-H44C109.5

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