Potential Spin Crossover and Valence Tautomerism of Hetero-nuclear Inverse Sandwiches [M(AIP)](C5H5)[M'(AIP)](M, M'=V, Cr, Mn) †

doi:10.7503/cjcu20190280

Abstract

Abstract:

The inverse sandwiches [M(AIP)](C₅H₅)[M'(AIP)](M, M'=V, Cr, Mn; AIP=dehydro-genated-1-amino-3-imino-prop-1-ene anion, C₃N₂ $H 5 -$ ) were theoretically studied. The calculated results show that V-Cr system has the quintet, septet, and nonet multistable states; and Cr-Mn system has the triplet, quintet and septet multistable states. In these systems, the valence states of metal atoms vary with the spin states of isomers, the variable valence states of +1 and +2 could be observed in V, Cr and Mn atoms. Due to the low spin crossing barriers between some bistable states of V-Cr and Cr-Mn systems, the spin crossover and valence tautomerism become possible. Since [M(AIP)](C₅H₅)[M'(AIP)] not only performs the spin crossover and valence tautomerism, but also has the stability against dissociation, these molecules are potential candidate for molecular magnetic materials.

Key words: Low valent, Nacnac ligand, Spin multiplicity, Multistable state

CLC Number:

O641

TrendMD:

LIU Nannan, WANG Jian. Potential Spin Crossover and Valence Tautomerism of Hetero-nuclear Inverse Sandwiches [M(AIP)](C₅H₅)[M'(AIP)](M, M'=V, Cr, Mn) ^†[J]. Chem. J. Chinese Universities, 2019, 40(10): 2128.

Figures/Tables 4

References 23

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Species	Product	ΔE/(kJ·mol^-1)	Product	ΔE/(kJ·mol^-1)
V-Cr-Q→	[V(AIP)]-S + [Cr(AIP)](C₅H₅)-Q	—	[Cr(AIP)]-D + [V(AIP)](C₅H₅)-Qu	246.4
	[V(AIP)]-T + [Cr(AIP)](C₅H₅)-T	236.7	[Cr(AIP)]-Qu + [V(AIP)](C₅H₅)-D	219.9
	[V(AIP)]-Q + [Cr(AIP)](C₅H₅)-S	—	[Cr(AIP)]-Sex + [V(AIP)](C₅H₅)-D	161.5
V-Cr-Sep→	[V(AIP)]-T + [Cr(AIP)](C₅H₅)-Q	273.3	[Cr(AIP)]-Qu + [V(AIP)](C₅H₅)-Qu	162.4
	[V(AIP)]-Q + [Cr(AIP)](C₅H₅)-T	164.8	[Cr(AIP)]-Sex + [V(AIP)](C₅H₅)-D	160.0
V-Cr-Nonet→	[V(AIP)]-Q + [Cr(AIP)](C₅H₅)-Q	148.4	[Cr(AIP)]-Sex + [V(AIP)](C₅H₅)-Qu	85.5
Cr-Mn-T→	[Cr(AIP)]-D + [Mn(AIP)](C₅H₅)-D	263.1	[Mn(AIP)]-S + [Cr(AIP)](C₅H₅)-T	—
	[Cr(AIP)]-D + [Mn(AIP)](C₅H₅)-Qu	264.3	[Mn(AIP)]-T + [Cr(AIP)](C₅H₅)-S	—
	[Cr(AIP)]-Qu + [Mn(AIP)](C₅H₅)-D	180.6	[Mn(AIP)]-T + [Cr(AIP)](C₅H₅)-Q	183.2
	[Cr(AIP)]-Qu + [Mn(AIP)](C₅H₅)-Sex	216.5	[Mn(AIP)]-Q + [Cr(AIP)](C₅H₅)-T	111.4
	[Cr(AIP)]-Sex + [Mn(AIP)](C₅H₅)-Qu	122.2	[Mn(AIP)]-Sep + [Cr(AIP)](C₅H₅)-Q	105.6
Cr-Mn-Q→	[Cr(AIP)]-D + [Mn(AIP)](C₅H₅)-Qu	299.2	[Mn(AIP)]-S + [Cr(AIP)](C₅H₅)-Q	—
	[Cr(AIP)]-D + [Mn(AIP)](C₅H₅)-Sex	333.9	[Mn(AIP)]-T + [Cr(AIP)](C₅H₅)-T	216.0
	[Cr(AIP)]-Qu + [Mn(AIP)](C₅H₅)-D	215.6	[Mn(AIP)]-Q + [Cr(AIP)](C₅H₅)-S	—
	[Cr(AIP)]-Sex + [Mn(AIP)](C₅H₅)-D	157.2	[Mn(AIP)]-Sep + [Cr(AIP)](C₅H₅)-T	138.5
Cr-Mn-Sep→	[Cr(AIP)]-D + [Mn(AIP)](C₅H₅)-Sex	315.0	[Mn(AIP)]-T + [Cr(AIP)](C₅H₅)-Q	199.2
	[Cr(AIP)]-Qu + [Mn(AIP)](C₅H₅)-Qu	197.8	[Mn(AIP)]-Q + [Cr(AIP)](C₅H₅)-T	127.4
	[Cr(AIP)]-Sex + [Mn(AIP)](C₅H₅)-D	138.2	[Mn(AIP)]-Sep + [Cr(AIP)](C₅H₅)-S	—

Species	Product	ΔE/(kJ·mol^-1)	Product	ΔE/(kJ·mol^-1)
V-Cr-Q→	[V(AIP)]-S + [Cr(AIP)](C₅H₅)-Q	—	[Cr(AIP)]-D + [V(AIP)](C₅H₅)-Qu	246.4
	[V(AIP)]-T + [Cr(AIP)](C₅H₅)-T	236.7	[Cr(AIP)]-Qu + [V(AIP)](C₅H₅)-D	219.9
	[V(AIP)]-Q + [Cr(AIP)](C₅H₅)-S	—	[Cr(AIP)]-Sex + [V(AIP)](C₅H₅)-D	161.5
V-Cr-Sep→	[V(AIP)]-T + [Cr(AIP)](C₅H₅)-Q	273.3	[Cr(AIP)]-Qu + [V(AIP)](C₅H₅)-Qu	162.4
	[V(AIP)]-Q + [Cr(AIP)](C₅H₅)-T	164.8	[Cr(AIP)]-Sex + [V(AIP)](C₅H₅)-D	160.0
V-Cr-Nonet→	[V(AIP)]-Q + [Cr(AIP)](C₅H₅)-Q	148.4	[Cr(AIP)]-Sex + [V(AIP)](C₅H₅)-Qu	85.5
Cr-Mn-T→	[Cr(AIP)]-D + [Mn(AIP)](C₅H₅)-D	263.1	[Mn(AIP)]-S + [Cr(AIP)](C₅H₅)-T	—
	[Cr(AIP)]-D + [Mn(AIP)](C₅H₅)-Qu	264.3	[Mn(AIP)]-T + [Cr(AIP)](C₅H₅)-S	—
	[Cr(AIP)]-Qu + [Mn(AIP)](C₅H₅)-D	180.6	[Mn(AIP)]-T + [Cr(AIP)](C₅H₅)-Q	183.2
	[Cr(AIP)]-Qu + [Mn(AIP)](C₅H₅)-Sex	216.5	[Mn(AIP)]-Q + [Cr(AIP)](C₅H₅)-T	111.4
	[Cr(AIP)]-Sex + [Mn(AIP)](C₅H₅)-Qu	122.2	[Mn(AIP)]-Sep + [Cr(AIP)](C₅H₅)-Q	105.6
Cr-Mn-Q→	[Cr(AIP)]-D + [Mn(AIP)](C₅H₅)-Qu	299.2	[Mn(AIP)]-S + [Cr(AIP)](C₅H₅)-Q	—
	[Cr(AIP)]-D + [Mn(AIP)](C₅H₅)-Sex	333.9	[Mn(AIP)]-T + [Cr(AIP)](C₅H₅)-T	216.0
	[Cr(AIP)]-Qu + [Mn(AIP)](C₅H₅)-D	215.6	[Mn(AIP)]-Q + [Cr(AIP)](C₅H₅)-S	—
	[Cr(AIP)]-Sex + [Mn(AIP)](C₅H₅)-D	157.2	[Mn(AIP)]-Sep + [Cr(AIP)](C₅H₅)-T	138.5
Cr-Mn-Sep→	[Cr(AIP)]-D + [Mn(AIP)](C₅H₅)-Sex	315.0	[Mn(AIP)]-T + [Cr(AIP)](C₅H₅)-Q	199.2
	[Cr(AIP)]-Qu + [Mn(AIP)](C₅H₅)-Qu	197.8	[Mn(AIP)]-Q + [Cr(AIP)](C₅H₅)-T	127.4
	[Cr(AIP)]-Sex + [Mn(AIP)](C₅H₅)-D	138.2	[Mn(AIP)]-Sep + [Cr(AIP)](C₅H₅)-S	—

Potential Spin Crossover and Valence Tautomerism of Hetero-nuclear Inverse Sandwiches [M(AIP)](C₅H₅)[M'(AIP)](M, M'=V, Cr, Mn) ^†

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