Polycyclic energetic compounds with high nitrogen content have attracted much attention owing to their distinctive advantages in constructing novel energetic molecules with low mechanical sensitivity， good thermal stability and high density. The construction of polycyclic skeletons involves the incorporation of tetrazole into fused heterocycle， serving as high-energy organic fuel and hydrogen bond donors. Three self-assembled non-hydrated energetic compounds， namely 7-amino-6-（2H-tetrazol-5-yl）-pyrazolo［1，5-a］pyrimidine （1）， 7-diamino-6-（2H-tetrazol-5-yl）-［1，2，4］triazolo［1，5-a］pyrimidine perchlorate （2）， and 2，7-diamino-6-（2H-tetrazol-5-yl）-［1，2，4］triazolo［1，5-a］pyrimidine perchlorate （3）， were synthesized through noncovalent self-assembly of polycyclic skeleton with the oxidizing structural unit HClO₄ rich in hydrogen bond acceptors. The structural characterization employed Nuclear Magnetic Resonance Spectroscopy and single crystal X-ray diffraction， while thermal behaviors and mechanical sensitivities were determined by differential scanning calorimetry-thermogravimetry and BAM methods. Detonation performances were predicted utilizing the Gaussian 09 program and EXPLO5 V6.05.02. The results show that three compounds exhibit high crystal densities （ρ： 1.75-1.86 g·cm^-3）， good thermal stabilities （decomposition temperature （onset）： 184-260 ℃）， and good detonation performances （detonation velocity： 7343-7570 m·s^-1； detonation pressure： 21.1~22.8 GPa）， surpassing those of traditional explosives trinitrotoluene （TNT）. Both compound 1 （impact sensitivity （IS） > 40 J， friction sensitivity （FS）=216 N） and compound 3 （IS=25 J， FS = 240 N） exhibit low mechanical sensitivity.