BCl3 does not exist as dimer but BH3 exists as dimer as dimer B2H6 because, large sized chlorine atoms do not fit in between the small boron atoms where as small sized hydrogen atoms get fitted in between boron atoms
Because of its instability it exists as a dimer, B2H6, where electrons are shared between each of the monomers. It is a gas, but is used in chemistry as solutions in THF, pyridine or dimethyl sulfide. In these solutions the lone pair of electrons from the oxyge, nitrogen or sulfur, are donated to the empty p orbital of boron, stabilising the BH3: solvent complex.