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, , ( , , () () ..), .
[2 2]- () - - () ( - -, - ).
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1. [4(^-)4()4(')4]4+ [4(/-)4()4(")2]4+ (, ' - , " - ). - , . .
2. - (1^)2 ( ). - ( = ) - ( = ^ , ) .
. - [2 2]- () -. , ( ) . , , , .
,
-.
- . - [ ]- , . , - .
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1. - [2 * 2]- () CN-.
2. ; ; .
. . , , .
. 10- 12- . . . (, 2006, 2009), VII , , - XXI (, 2007), IV V (, 2008; , 2010), VI (, 2009), IX XXI (, 2010), IV International conference on molecular materials (Montpellier, 2010), III EuCheMS chemistry congress Chemistry - the creative force (Nürnberg, 2010), (, 2010).
. 3 , , 10 .
. 117 , 18 12 , , , , , 181 . , ( 1.1) ( 1.2) . ( 2.1), - ( 2.2), ( 2.3). , , 2.4. .
. . .
- (a) PRIRODA () GAUSSIAN : (a) 3z (2-) L2 ( cc-pVTZ) () S VP / TZVP. [2 2]- () CN- /3 z//PBE/L2. (
- , H = -2^[jJij(Si-SJ),
< j
) ( ,
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). HS- BS- B3LYP SVP / TZVP, .
. ( ) SHAPE.
- [2 2]- () CN-
4+
(L)N4FeC=NFeN4(L*)
N
Mi III
N
I 4 3 I
(L*)N4FeN=C FeN4(L)
. 1. 1-6.
. 1 (* = V V). ( *). - - (). - , , (^), -. - 1:
[4(-)4()]4+ = , V = 1
[4-)4()4()4]4+ = , V = 2
[4(-)4()4(1)2] = , " = 1 3
[4(-)4()4(1)2]4+ = , " = 1 4
[4-)4()4(-1)2]4+ = , " = -1 5
[4-)4()4(2-1)2]4+ = , " = 2-1 6
()-. . 1(6)4-420 - ( 300
1 - 2,2-, - 2,2'-, phen - 1,10-, tpma -
(2-), Me-tpma - ((6--2-))(2-
), Me2-tpma - ((6--2-))(2-).
)2. 2(PF6)4-6CH30H-4H20, bpym- , [LS-LS] <- [HSHS], ( > 400 ). 3(PF6)4, tpma- , [LS-LS] <- [HS-LS] - [HS-HS] (Tm(\) = 160 , Th2(2) ~ 380 )4. 4 phen- 3 (bpy- phen-)5. , 4()4 , 3(PF6)4, [LS-LS] *-* [HS-HS], 4(PF6)4 Ti/2(2) 3(PF6)4. 5(PF6)4 6(PF6)4-NH4PF6 4(PF6)4, - tpma-5. HS- . . , - 1 6. - , , , .
[LS-LSJ-, [HS-LS]- [HS-HS]-
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[LS-LS]-, [HSLS]- [HS-HSJ-6 :
() FeNe- .
2 . Oshio, . Onodera, . Tamada, . Mizutani, . Hikichi, . Ito // Chem. Eur. J. - 2000. -V. 6.-P. 2523-2530.
3 M. Nihei, M. Ui, H. Oshio // Polyhedron. - 2009. - V. 28. -P. 1718-1721.
4 M. Nihei, M. Ui, M. Yokota, L. Han, A. Maeda, H. Kishida, H. Okamoto, H. Oshio if Angew. Chem., Int. Ed. - 2005. - V. 44. - P. 6484-6487.
51. Boldog, F. J. Muñoz-Lara, A. B. Gaspar, M. C. Muñoz, M. Seredyuk, J. A. Real // Inorg. Chem. -2009. -V. 48. -P. 3710-3719.
6 [HS-HS]-moMepoB ( , ).
() , [HS-LS]-. , 1-6, [HS-HS]- [HS-Lsj- ( ), - , HS- [HS-LSJ-. [LS-LS]- [HS-LSJ- - , LS- [HS-LSJ-. , , , FeN4C2 .
1. , [LS-LS]-, [HS-LS]- [HS-HSJ- 1-6
, ( ).
1 0.0 93.8 186.8
2 0.0 92.0 186.1
3 0.0 74.1 147.5
4 0.0 75.0 147.3
5 0.0 58.0 109.9
6 0.0 34.8 67.0
. 1. _[LS-LS]-[HS-LS]-[HS-HS]
[LS-LS]- ( ) .
, (. ). , 5 6, .
[HS-LS]- , [LS-LS]- [HS-HS]-7. 1-6 - , (. ). , . 1 , [HS-LSJ-
7 J. . Real, . Bolvin, . Boussesksou, . Dworkin, . Kahn, F. Varret, J. Zarembowitch J. Am. Chem. Soc. - 1992. - V. 114. - P. 4650-4658.
[LS-LS]- [HS-HS]-, .
, , 1-6 ( ) . , . , .
. 3 4 . tpma- , 3(PF6)4 4(PF6)4 - 4(PF6)4 , 3(PFi)4 . . , 3(PF6)4, [LS-LS]- [HS-LSj-, tpma- Fe(2), , - , Fe(2)-N-C 180. Fe(2)-N. , tpma- Fe(4) . , , , Fe(2) Fe(4). 4(PFC)4, [LS-LS]- [HS-HS]-, . , [HS-LS]- , , 3(PF6)4.
|
|
2.
(. 2) (2) (4) 8 3 (
3 , (4)
, (2) .
Fe(2) Fe(4)
100 0.58 0.31
[LS-LS] (0.31) (0.31)
300 1.83 0.33
[HS-LS] (1.29) (0.30)
[HS-HS] (1.30) (1.30)
, Fe(4) LS- . Fe(2). 300 , HS- . . (100 ) , LS-, . , , 3(PF6)4 .
[HS-HS]-
, , , [HS-HSj-. [HS-HSJ- 5 = 0, 1, 2, 3 4. , CN- , 1-6 [()2()2]-, [HS-HSJ- . , J ( ) 0.15 '1.
8 .
( = 4) (5 = 0) 3 " (0.04 -"'). , , [-8]-, , .
- ()2
- ΄_, . , , , , . - ΄?^ , , . - , 9 - - , - .
-
- ()2. (. 2, ) - , . 051.
9 . . , . . , . . , . ., , . . , . . , . . // . , . - 2002. - . 43. - . 163-179; . . , . . , . . , . . , . . , . . // . . . . - 2004. - . 2304-2325.
N
()2^ { ^^^^^^^4.^
............'
7
. 2. - () _ - ()._
^ (1^)2 . -- 2+-{0'-} ( > 0), -<\ -2.4 ( - -). - - - -2.0 , (/ 0) ( -).
- , ()2 . ( > 7) - (, = 31 "1, /2 = 15 "1). () () , . , .
( < 7) - (^ = -873 "1). - () . , . , - (72 = 16 "1), .
( ): = 0.5/1 + 0.5/2, -
. //), ,
10.
-
- (. 2, ) - 06 042. , , . - , 2+ ^^.
- -. - -- (- -2.3 ), {^-'0}-2+-{0'-} , (4£ < \ < 22). - -^ - (~2.0 ) ./. - (22 < 2£| <4) .
^ -^
.
150 200 250 300 /
. 3. ()2 = 2.15, . = 2.0).
"4////< = 798(/,0(7)"2 () = 2.828(,7)1 ().
-. -: Cu-Ol (2.311 ), -& (1.971-1.984 ). 44 "1 (Cu2+-{0'-N), J) -5 "1 ({N-'O}...{O'-N}, J), -. , 164 , . fiejgr . -, , - - , .. - 11. . , 163 Cu-Ol (2.311 > 2.248 ), Cu-Ohfac Ohfac-Cu-Ohfac (1.984 * 2.022 ). , . :
d=wdAf + (l-w)dF, (1)
dAY. dr - , a w (1 -w) - - - . , -.
150, 140, 130, 120 110 . , CUO4N2. 150-110 . , 06
" V. I. Ovcharenko, G. V. Romanenko, . Yu. Maryunina, A. S. Bogomyakov, E. V. Gorelik // Inorg. Chem. - 2008. - V. 47. - P. 9537-9552.
. , , . CuOe . 06 - (J? = \ "1, J? = -5 "), -- (Jaf = -767 "1, Jaf = -22 "1).
d cfp, - (1) . 295 9% CuOe -, 163 - 25.4%. , - . (164 ) ( < 150 ) , w 0.5 . , -, .
{Cu(hfac)2LBu-0.5C6H14} ( ): Xrrtol 0 ex Q^Xmono> ~
2+ CUO4N2, ~
06 - -: = wxaf + -
2,60
2,55 ^. *
2,50
^ 2,45
^ 2,40 V
2,35 ♦
2.30
50 100 150 100 250 300
11
. 4.
()2-0.514
tecu = 2.15, *L = 2.0).
()20.5614 '(7) . - - ¡^/) .
^^1* ^^ܮ , , -12. , -, , g- - - , - (^-, , 12. - - (|7| < 10 "1)12. , , - - - (^-, \-12.
1. , [2 2]- () - [8]-. .
2. , [-]- , .
12 . . , . . , . 3. , . . , . . // . . . . - 2010. - . 1043-1058; . V. , 8. . , . . , . V. , . . , N. . ., . . Sagdeev, V. I. , . . //1. . . . - 2010. - V. 132. - . 13886-13891; . . , . V. 1, . . , . 1, . , . , W. 1, . . Sagdeev, V.
I. , . . Bagryanskaya//- . - 2011. - V. 50.-. 10204-10212.
3. - Cu(hfac)2LR ( ), -.
4. .
5. CuOjN ( -) ( -). , .
:
, :
1. . . - () / . . , . . , . . // . . . .-2009,-8.-. 1605-1613.
2. Zueva . . Spin crossover in tetranuclear cyanide-bridged iron(II) square complexes: a theoretical study / E. M. Zueva, E. R. Ryabikh, An. M. Kuznetsov, S. A. Borshch Inorg. Chem. - 2011. - V. 50. - 5. - P. 1905-1913.
3. Zueva E. M. Theoretical analysis of spin crossover in iron(II) [2 x 2] molecular grids / E. M. Zueva, E. R. Ryabikh, S. A. Borshch // Inorg. Chem. - 2011. - V. 50.-21.-P. 11143-11151.
:
4. E. M. - () : - / . . , . . , . . // 10- . . . . , 2006. - . 65.
5. . . () / . . , . . , . . // VII , , - XXI . - , 2007. - . 103.
6. Zueva . . The local spin transitions in polymeric chain copper(II) complexes with nitronyl nitroxide radicals: situations when the isotropic exchange model cannot be applied / E. M. Zueva, E. R. Ryabikh, An. M. Kuznetsov // Book of
abstracts of IV International conference High-spin molecules and molecular magnets. - Ekaterinburg, 2008. - P. 106.
7. . P. () / . . , . . , . . // VI . - , 2009. - . 133.
8. . . - - () / . . , . . , . . , . . // 12- . . . . -, 2009. - . 19.
9. . . - () - / . . , . . , . . , . . // IX XXI . - , 2010. - . 1. - . 5.
10. Zueva . . Quantum-chemical studies of iron cyanide-bridged squares with spin crossover / E. M. Zueva, E. R. Ryabikh, An. M. Kuznetsov, S. A. Borshch // Book of abstracts of IV International conference on molecular materials. -Montpellier, 2010. (PI 16).
11. Borshch S. A. Spin crossover in cyanide-bridged iron(II) squares: theoretical analysis / S. A. Borshch, E. M. Zueva, E. R. Ryabikh, An. M. Kuznetsov // Book of abstracts of III EuCheMS chemistry congress Chemistry - the creative force. - Nürnberg, 2010. (VIIc.020).
12. . P. - (), - / . . , . . , . . , . . // V . - , 2010. (035).
13. . . () / . . , . . , . . , . . // . - , 2010.-. 84.
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