For an associative algebra $A$ one can define the Hochschild cohomology of $A$ as $ HH^n(A,A):= Hom\_{\mathcal{D}(A^{op} \otimes A)}(A, [n]A)$ (this definition also works for the graded and dg cases as well). There is a lot of information contained in this gadget: when $ n=0$ it is the center and when $n=1$ it is the lie algebra $\text{Der}(A)/\text{Inn}(A)$ and when $n=2$ it says something about the deformation theory of the algebra. Also there is a cup product and Gerstenhaber bracket on $HH^\*(A,A)$.


My question is: What is the reason/motivation for the definition $ HH^n(A,A):= Hom\_{\mathcal{D}(A^{op} \otimes A)}(A, [n]A)$, if you didnt know about all this higher structure what would lead you to study it in the first place?



Motivation behind the definition of hochschild cohomology
I think you will have different answers to your questions. As you noticed there is more about Hochschild Homology in n-lab page and you also pointed out the interpretation of (positive) low dimension of Hochschild cohomology. I would say that the Hochschild cohomology is "The" cohomology theory for differential graded algebras in the following sense.
Let $\mathsf{dgAlg}\_{k}^{\geq 0}= \mathsf{A}$ be the category of (connective) differential graded algebras over a commutative ring $k$, which is a model category . Fix a morphism of DG $k$-algebras $f:R\rightarrow S $ with $R$ cofibrant DGA, then the homotopy groups of the mapping space $Map\_{\mathsf{A}}(R,S)\_{f}$ are closely related to the (negative) Hochschild cohomology $HH^{-\ast}(R,S)$ where you see $S$ as an $R$-bimodule via $f$. More precisely, for all $i>1$:
$$\pi\_{i}Map\_{\mathsf{A}}(R,S)\_{f}\cong HH^{1-i}(R,S). $$
In the particular case $id:R\rightarrow R$, we can say more i.e., 
$\pi\_{1}Map\_{\mathsf{A}}(R,R)\_{id} $ is a subgroup of the units group of the algebra $HH^{0}(R,R)$ (i.e., $HH^{0}(R,R)^{\times}$).


Block and Lazarev gave an interpretation of the (negative) Andre-Quillen cohomology in the case of commutative differential graded $\mathbf{Q}$-algebras denoted by $\mathsf{C}$. 
$$ \pi\_{i}Map\_{\mathsf{C}}(R,S)\_{f}\cong AQ^{-i}(R,S), i>1. $$


