Combining
[Ni(phen)3]I2 or [Ni(phen)3]Cl2 (phen = 1,10-phenanthroline) with the iodoperfluorobenzenes
(IPFBs), 1,2-, 1,3-, 1,4-diiodotetrafluorobenzene (1,2-, 1,3-, and
1,4-DITFB, respectively), or 1,3,5-triiodotrifluorobenzene (1,3,5-TITFB)
resulted in the formation of six different cocrystalline materials
featuring halogen-bonded networks encapsulating [Ni(phen)3]2+ ions. The cocrystals have the general formula [Ni(phen)3][(IPFB)
n
(X2)(L)
m
]·solvate (n = 2 or 3; X = Cl– or I–; L = halogen-bonded H2O and/or MeOH; solvate = isolated
H2O and/or MeOH). The halide ions balance the charge of
the metal complexes and simultaneously act as halogen bond acceptors
for the electronically polarized iodine atoms of the IPFB donors.
The structures display a wide variety of supramolecular motifs in
the context of both the aggregation of the metal complexes and the
topology and connectivity of the halogen bond networks. The well-known
supramolecular “aryl embrace” motifs of [Ni(phen)3] complexes are present but are structurally compromised to
varying degrees in the crystals of [Ni(phen)3][(1,2-DITFB)2I2]·MeOH, [Ni(phen)3][(1,3-DITFB)2I2]·2MeOH, and [Ni(phen)3][(1,3-DITFB)2(H2O)2Cl2]·1.5MeOH.
In [Ni(phen)3][(1,3-DITFB)3I2], the
[Ni(phen3]2+ complexes are so thoroughly enclosed
in halogen-bonded networks that the metal complexes have no significant
supramolecular contact. In contrast, in [Ni(phen)3][(1,4-DITFB)3I2(MeOH)0.5] and [Ni(phen)3][(1,3,5-TITFB)2Cl2] the complexes are arranged
in typical aryl embrace motifs (pairwise and 1D chains, respectively),
but with adjacent complexes held in closer proximity to each other
than they reside in crystals of the pure metal complex. The interplay
between the supramolecular chemistry of the halogen-bonded networks
and the metal complexes was examined in detail, and the results demonstrate
that it is possible to significantly influence the aggregation of
metal complexes by encapsulation in different halogen bond networks.