In optoelectronic devices, chromophores can be designed at the molecular level to create materials with properties desired for advanced applications. Organic fluorophores in particular can be constructed with macroscopic properties that arise from two distinct contributions: (i) the collective impact of the molecular backbone and substituents and (ii) the connectivity within the molecule (that is, the spatial molecular architecture). Accordingly, the exploration of novel conjugated architectures is a productive area of current research. Different two-dimensional, "X-shaped" conjugated materials have been synthesized for a variety of applications. They include spiro compounds, paracyclophanes, swivel-type dimers, bisoxazole-derived cruciforms, tetraethynylethenes, and tetrasubstituted tolanes. A subset of these compounds are constructed from two "perpendicular" pi-conjugated linear arms connected through a central aromatic core; examples of these include tetrakis(arylethynyl)benzenes, tetrakis(styryl)benzenes, and tetrasubstituted thiophenes. In this Account, we evaluate 1,4-distyryl-2,5-bis(arylethynyl)benzenes or cruciforms (XFs). Electronic substitution of this "X-shaped" cross-conjugated scaffold tunes both the energy levels of the frontier molecular orbitals (FMOs) and their spatial distribution in XFs. The resulting fluorophores exhibit FMO separation, imbuing XFs with unusual yet desirable properties for sensory applications. Using model analytes, we examine how the underlying FMO arrangement and the nature of analyte interaction elicit observable responses. These studies provide a foundation for accessing functional responsive ratiometric cores, demonstrating the importance and unique potential of FMO-separated fluorophores. We also highlight the essential contribution of serendipity in materials development. Moving beyond one-dimensional molecular wire-type fluorophores to two-dimensional "X-shaped" materials provides access to materials with unexpected and exciting properties. XFs represent such novel conjugated architectures, and their successful development has frequently has hinged on inspiration from structural components and principles developed in diverse research areas.

The photophysics of dialkylamino- and/or pyridine-containing functional chromophores, 1,4-distyryl-2,5-bis(ethynylaryl)benzenes (cruciforms) was investigated; their fluorescence quantum yields and emissive lifetimes were determined. Depending upon their substituents, the frontier molecular orbitals (FMOs) of these cruciforms are either congruent, i.e., HOMO and LUMO occupy the same real space, or disjoint, i.e., the HOMO is located on one branch of the cruciform while the LUMO is located on the second one. Donor-acceptor substitution leads to a disjoint FMO pattern, while the parent 1,4-distyryl-2,5-bis(phenylethynyl)benzene shows congruent FMOs. The photophysics of the cruciforms was investigated upon addition of either an excess of trifluoroacetic acid or an excess of selected metal (Mg(2+), Ca(2+), Mn(2+), Zn(2+)) trifluoromethanesulfonate salts. Addition of either metal ions or protons led to analogous but not identical changes in the spectroscopic properties of the investigated cruciforms. The collected data suggest that the metals bind preferentially at the aniline nitrogen and not at the electron-rich arene. The spatially separated FMOs permit the independent manipulation of the HOMO and the LUMO of such cruciforms. If the branches contain metal-complexing moieties, metal binding leads to either a hypsochromic or a bathochromic shift in emission via interaction of the metal cations with either the HOMO or the LUMO.

By self-assembling fluorescent pyridyl cruciforms with bis-Pd-pincer complexes, supramolecular assemblies with attractive optical properties were synthesized; these assemblies show potential as electro-optical materials.

We report the synthesis and characterization of five novel phenothiazine-containing cruciforms (5-9). The targets were prepared by a NaH-promoted Horner reaction of tetraethyl(2,5-diiodo-1,4-phenylene)bis(methylene)diphosphonate with 10-hexyl-10H-phenothiazine-3-carbaldehyde. The formed intermediary 3,3'-(1E,1'E)-2,2'-(2,5-diiodo-1,4-phenylene)bis(ethene-2,1-diyl)bis(10-hexyl-10H-phenothiazine) was reacted with several different aromatic alkynes (1-tert-butyl-4-ethynylbenzene, N,N-dibutyl-4-ethynylaniline, 1-ethynyl-3-(trifluoromethyl)benzene, and 1-ethynyl-3,5-bis(trifluoromethyl)benzene) to give the corresponding cruciform fluororphores (XF). The XFs were fully characterized by NMR and IR spectroscopy and then exposed to trifluoroacetic acid as well as to several metal triflates. The XFs show dramatic shifts in emission and to a lesser extent in absorption when exposed to magnesium triflate or zinc triflate. In the case of magnesium triflate, a blue shift in emission was observed; in contrast, addition of zinc triflate results in either quenching or a red-shifted emission. Due to the electronic situation, these XFs display spatially separated frontier molecular orbitals, allowing the HOMO or the LUMO of the XFs to be addressed independently by addition of zinc or magnesium ions. Phenothiazine XFs may have potential in array-type sensory applications for metal cations.