Recent works demonstrated that the structure of self assembled monomers can be engineered. Subsequently, performance in polymer-network assemblages of such monomers can be enhanced through microstructural design. This work presents a multiscale analysis of polymers comprising flexible V-shaped monomers. We show that two mechanisms enable the deformation of a chain: conformational entropy and elastic energy stemming from the monomers deformation. The mechanical behavior of a polymer network is obtained through an integration from the chain to the network level. We demonstrate that the shear modulus, the extensibility limit of the network, and the force elongation response can be tuned by manipulation of the V-shaped monomer structure. As an example, the range of properties that can be achieved in an elastomer comprising 4-arm nanostar monomers subjected to uniaxial extension is examined. We find that appropriate manipulation of the monomer structure can lead to anywhere between an-400% decrease to an 40% increase in the shear modulus and the extensibility limit.