Significant progress has been made in the field of luminescent materials having efficient ambient triplet harvesting for applications in organic light-emitting diodes (OLEDs), bioimaging and photo-catalysis. In this regard, triplet harvesting via thermally activated delayed fluorescence (TADF) has emerged as a challenger technology to the incumbent roomtemperature phosphorescence in OLEDs. The efficiency of TADF relies in part on minimizing the energy gap between the lowest excited singlet and triplet states. This is usually achieved using donor-acceptor charge-transfer chromophores, where orthogonally oriented D and A units, i.e. twisted D-A molecules, minimises the electron exchange energy and therefore the splitting between the lowest excited singlet and triplet states, provided they exhibit the same spatial symmetry. Different strategies have also been used to realize this objective, including spiro-linked D and A, arranging D and A in spatial proximity to achieve through-space charge transfer, or forming molecular exciplexes. One of the primary concerns with twisted D-A molecules is stability during device operation, as TADF OLED lifetimes are as yet very limited. To achieve high stability in an OLED, it is believed that all rotationally flexible tertiary N-C bonds must be removed from all molecules including TADF molecules as these are the weakest chemical bonds present in their structure and therefore prone to degradation. It is hoped that spiro-type TADF emitters, especially used in hyperfluorescence, could overcome this, as recently demonstrated by Stavrou et al., but as yet they also have not demonstrated great lifetime improvement. Fully rigid structures should result in far more stable molecules, offering high rates of fluorescence and short CT lifetimes with negligible energy dispersion. The latter is very large in the flexible twisted D-A molecules because of distributions of the twist angles which result in long-lived TADF components detrimental to OLED operational lifetime. However, the main obstacle to exploiting a fully rigid D-A molecular structure is the inherent planarity and conjugation which is believed to make intramolecular charge transfer (ICT) improbable. There has been a significant amount of work developing the short-range charge transfer associated with the multi-resonance (MR-TADF) approach. However, while this has achieved exciting results, it represents an entirely new framework with a limited chemical space due to molecular design restrictions required to achieve MR-TADF. In addition, to date, these emitters often exhibit slow rates of reverse intersystem crossing (rISC) and therefore, are useful only as hyperfluorescence end-acceptors where typically D-A TADF emitters act as FRET (Förster Resonance Energy Transfer) sensitizers. With the objective of achieving desirable rigidity, low CT dispersion energies and high fluorescence rates, our research explored an unconventional pathway of utilising rigidly planar D-A molecules that give unexpected ambient triplet harvesting. Previously, a few rigidified aminobenzonitriles have shown ICT states without the need of a large-amplitude rotational motion required to form a twisted conformation. However, the stability of these co-planar ICT states depend on the energy gap and coupling between the low-lying singlet states, and ICT emission is observed only in highly polar solvents, albeit no triplet contribution has ever been reported. To the best of our knowledge, a fully-conjugated, co-planar and rigidified donor-acceptor chromophore giving strong ICT emission involving both singlet (prompt fluorescence) and triplet excited state (TADF) in non-polar environments has not been observed. Rajamalli et al. proposed a D-A-D system showing TADF which they claimed was planarized through hydrogen bonding between D and A. Subsequently, Chen et al. and He et al. invoked similar D-A hydrogen bonding schemes in HMAT-TRZ and ICZ-TRZ, respectively for potential TADF design strategy. However, both these derivatives show large ∆EST (>0.43 eV) and do not show any TADF in dilute non-polar zeonex films, hinting towards triplet-triplet annihilation (TTA) or weak exciplex derived TADF when doped in appropriate hosts at high doping concentrations. Notably, detailed potential energy surface analysis combined with experimental time-resolved spectroscopy studies on several model 'intramolecular H-bond' containing D-A molecules by Hempe et al. and Bergmann et at. suggested that such D-A hydrogen bonds are unlikely to form and drive the rISC process.