Cyclopropenium cyclopentadienide: a strangely neutral ion-pair?

Both the cyclopropenium cation and the cyclopentadienide anion are well-known 4n+2-type aromatic ions, but could the two together form an ion-pair?

A search of the Cambridge structure database reveals 52 instances of the cyclopropenium cation with a variety of counter-anions, 77 cyclopentadienide anions with a variety of counter-cations and one (SOWMOG, private communication to CSD) where the two sub-structures are common. The pyridinium-cyclopropenium fragment is actually a di-cation stabilized with dimethylamino substituents, with these charges balanced by two cyclopentadienide anions stabilized with ester substituents. The stacking distance between the ion-pairs is ~3.5-3.6Å, a bit larger than normal π-π stacking distances of 3.2-3.3Å

So could a “pure” cyclopropenium cyclopentadienide ion-pair exist, and if so what would its π-π stacking distance be? A ωB97XD/Def2-TZVPPD/SCRF=water calculation (DOI: 10.14469/hpc/2442) provides one answer to this question; 2.57Å!^‡ It is a true minimum in the potential energy surface (all +ve force constants) with a calculated dipole moment of only 7.57D. This species is “only” 27.1 kcal/mol higher in ΔG than the neutral hydrocarbon (DOI: 10.14469/hpc/2443), a difference which is as low as it is because of the gain in aromatic stabilization of two rings upon ion-pair formation.

A few posts back, I was considering candidates for the most polar neutral compound synthesized and I suggested a candidate with a dipole moment of ~22D, based as it happens on cyclopropenium and cyclopentadienide rings directly connected by a bond. So when this bond is removed and the two rings are allowed to stack one above the other, we now have an interesting inversion of the original challenge: what is the least-polar ionic organic compound (ionic in the sense of being an unconnected ion-pair)?

Here are some more properties of this intriguing “neutral” ion-pair.

1. It has a number of low-frequency modes with correspond to the two rings moving with respect to each other (ν 216 cm^-1)
   
2. The molecular electrostatic potential illustrates the sense of polarization, with negative region (orange) residing on the 5-membered ring:
3. The most stable π-type molecular orbital (below) reminds of the π-complex formed in the benzidine rearrangement and that in fact modelling this ion-pair may require a multi-reference (CASSCF) wavefunction, with the single-determinantal one used here only being a first approximation.
4. A QTAIM analysis of the electron density topology shows only weak “bond” connectors between the two rings, with ρ(r) being typical of weak interactions such as hydrogen bonds.
5. An ELF (electron localisation function) analysis also holds no surprises, with all the electron density basins (purple) confined to the two rings, just as expected of an ion-pair.
6. I will leave one further question to a future discussion; what happens to the aromaticity and ring currents of the two individual rings as they combine to form this ion-pair? Might this property be connected to the very close separation between the two rings?

So we have a remarkably “neutral” ionic hydrocarbon to match the “ionic” neutral organic molecules previously discussed. This ion-pair may yet prove to have interesting properties, even if is unlikely to be synthesized without the addition of stabilising substituents.

^‡ For example, the stacking distance in graphite is 3.35Å.