Mn^II(TCNE)_3/2(I₃)_1/2–A 3D Network‐Structured Organic‐Based Magnet and Comparison to a 2D Analog

Mean Field Analysis of the Exchange Coupling (J) for Two- and Three-Dimensional Structured Tetracyanoethenide (TCNE•–)-Based Magnets

“…Generalized bonding schemes for M(L S1 )(L S2 ) 1/2 of structure-type C 1 , and M(LS) 3/2 of structure-type C 2 . 8 ] 2− ; S = 5/2, S′ = 1/2), can be estimated from eq 4. Because only T c is known, J and K cannot be solved individually.…”

“…The sign of the inter-and intracoupling constants for compounds studied indicates antiferromagnetic coupling, as observed. 8 ] 1/2 , the intralayer coupling was assumed to be the same as compound [Mn(TCNE)(NCMe) 2 ] + since they share similar 2-D layers, and the interlayer coupling constant, K/k B , was estimated as −1.02 K for 2. This suggests that the interlayer interaction is antiferromagnetic and leads to bulk antiferromagnetic ordering, as observed.…”

“…With the initial goal to identify the exchange coupling within (J = J intra ) and between layers of 2-D and structurally bridged 2-D (3-D), as well as 3-D magnetic materials based their observed T c , an MF 11 The ordered anions reside in the channels (structure type A vide infra). 8 The ordered solvent and ordered I 3 − anion resides in the channels (structure type C 2 vide infra).…”

“…8,11,12,16,20 To be selfconsistent with our MF analysis, the same method, namely, the temperature at which the maxima in the frequency independent χ′(T) is used as T c . These values are listed in Table 1. MF theory is useful for predicting trends and for qualitative estimates of exchange constants.…”

Characterization of Tetracyanopyridine (TCNPy)‐Based Magnets: V[TCNPy]2⋅z (CH2Cl2) (Tc=111 K) and V[TCNPy]3⋅z (CH2Cl2) (Tc=90 K)

“…− (H 2 TPP= meso ‐tetraphenyporphryin), [Fe II (TCNE) . − (NCMe) 2 ] + [Fe III Cl 4 ] − , and Mn II [TCNE] 1.5 (I 3 ) 0.5 are examples of 1‐, 2‐, and 3 D extended structured materials with T c values of 18, 90, and 171 K, respectively. Furthermore, V[TCNE] x ⋅ z (CH 2 Cl 2 ) ( x =2; z= 0.5) has a T c exceeding room temperature (400 K; 127 °C) from the reaction of TCNE and V(CO) 6 either in dichloromethane or solvent‐free through chemical vapor deposition as thin films .…”