The tolane bridged nitronyl nitroxide biradicals with hydrogen bond donor and acceptor functional groups were synthesized. The magnetic measurements and the DFT calculations were performed to ascertain the influence of the functional groups on inter- and intramolecular magnetic exchange interactions. While upon functionalizing the tolane bridge the intramolecular exchange interactions remained nearly unchanged, the fine-tuning of intermolecular exchange interactions could be achieved by employing the crystal engineering approach.