The relationship between modal logic and graph theory has, indeed, been studied before. Peter mentioned sheaf models in the comments; I want to mention a more classical-logic-y perspective.
(First, let me note that when we say that $\phi$ characterizes a class of frames $V$, we mean that for every frame in $V$, and every valuation on that frame, $\phi$ is true, i.e., $\phi$ is a validity on every frame in $V$. There are frames together with valuations which satisfy, e.g., $\square p\implies \square \square p$ without the frame being transitive.)
It's a natural question to ask which properties of frames can be defined by propositional modal formulas. For example, as you mentioned in the question, we can characterize transitivity by a single modal formula. It turns out that the class of properties of frames which can be captured by modal formulas is substantially larger than the class of first-order-definable properties. Blackburn, de Rijke, and Venema's book ("Modal logic") gives the example of the Lob formula: $$ \square (\square p\implies p)\implies \square p$$ They show that this formula is a validity in precisely those frames in which the relation $R$ is transitive and well-founded (although they use the term "converse well-founded"). By a compactness argument, this class of frames is not first-order axiomatizable. A result of Goldblatt and Thomason in 1974 showed that "a first-order frame property is modally definable iff it is preserved under taking generated subframes, p-morphic frame images, disjoint unions, and inverse ultrafilter extensions." I don't really understand what all that means, but at the very least we can take away that not every first-order property of frames is characterized by a (propositional) modal formula.
In the other direction, since the definition of "valid modal formula" is second-order, it's clear that any class of frames which can be captured by a modal formula is definable in second-order logic. I recall a paper on the strength of modal logic that showed that a sort of converse to this held, despite the converse itself failing (since, as mentioned above, not even every first-order property of frames is modally definable) but I can't track it down at the moment. EDIT: Emil found it - it's "Reduction of second-order logic to modal logic" by S. K. Thomason, and a (very poor) copy can be found here: http://onlinelibrary.wiley.com/doi/10.1002/malq.19750210114/abstract.
In general, the book "Modal logics" by Chagrov and Zakharyaschev is probably the book to look at. I don't know how up-to-date it is anymore, but it seems to include every perspective on modal logics that I've heard of, short of the category-theoretic aspects.
EDIT: Another aspect, which I didn't think of at first, is given by alternate interpretations of modalities. For example, suppose we interpret $\square p$ as meaning "more than half of visible nodes satisfy $p$," instead of "all visible nodes satisfy $p$;" or some other interpretation. Under each interpretation, the classes of graphs we can charaterize by modal formulas changes; and while any specific alternate interpretation is probably not too interesting, general tools for studying that would probably be very deep and valuable. I don't know of any work on this, but I suspect it's been done before; the closest related source I can find at present is the extended abstract of "The Modal Logic of Probability" (Heifetz, Mongin) which seems vaguely along these lines.